CN101855759A - Multilayered sofc device on ceramic support structure - Google Patents

Multilayered sofc device on ceramic support structure Download PDF

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CN101855759A
CN101855759A CN200880115271A CN200880115271A CN101855759A CN 101855759 A CN101855759 A CN 101855759A CN 200880115271 A CN200880115271 A CN 200880115271A CN 200880115271 A CN200880115271 A CN 200880115271A CN 101855759 A CN101855759 A CN 101855759A
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fuel
zone
cell
anode
active
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A·德沃
L·德沃
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0297—Arrangements for joining electrodes, reservoir layers, heat exchange units or bipolar separators to each other
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
    • H01M8/1226—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material characterised by the supporting layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/1286—Fuel cells applied on a support, e.g. miniature fuel cells deposited on silica supports
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
    • H01M8/2425—High-temperature cells with solid electrolytes
    • H01M8/243—Grouping of unit cells of tubular or cylindrical configuration
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
    • H01M8/2425—High-temperature cells with solid electrolytes
    • H01M8/2435—High-temperature cells with solid electrolytes with monolithic core structure, e.g. honeycombs
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2465—Details of groupings of fuel cells
    • H01M8/2484—Details of groupings of fuel cells characterised by external manifolds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2465—Details of groupings of fuel cells
    • H01M8/2484—Details of groupings of fuel cells characterised by external manifolds
    • H01M8/2485—Arrangements for sealing external manifolds; Arrangements for mounting external manifolds around a stack
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/249—Grouping of fuel cells, e.g. stacking of fuel cells comprising two or more groupings of fuel cells, e.g. modular assemblies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The fuel cell device (10) includes one or more active layers containing active cells (24a, 26a, 24b, 26b) that are connected electrically in parallel. The fuel cell device (10) includes an elongate ceramic support structure (29) the length of which is the greatest dimension such that the coefficient of thermal expansion has only one dominant axis coextensive with the length.

Description

The multi-layer solid oxid fuel cell device that relates to ceramic support structure
The cross reference of related application
37. § 1.78 (a) (4) according to the United States Federal's code (C.F.R), it is the common unsettled provisional application No.60/986 of " Fuel Cell Device and System " that the application requires in the title of application on November 8th, 2007, the priority of 368 (attorney docket DEVOFC-06P).The title that the application also is involved in application on May 8th, 2008 is " Fuel Cell Device and System " common unsettled U.S. Patent application No.12/117,622 (attorney docket DEVOFC-05US1), its disclosed content integrally is incorporated into this by reference, the application also relates to the common unsettled U.S. Patent application No.11/747 that the title that is all application on May 10th, 2007 is " Solid Oxide Fuel Cell Device and System ", 066 (attorney docket DEVOFC-03US1) and No.11/747,073 (attorney docket DEVOFC-03US2), its disclosed content integrally is incorporated into this by reference.The application also relates to the common unsettled U.S. Patent application No.11/557 that the title that is same as application on November 8th, 2006 is " Solid Oxide Fuel Cell Device andSystem ", 894 (attorney docket DEVOFC-04US1), No.11/557,901 (attorney docket DEVOFC-04US2) and No.11/557,935 (attorney docket DEVOFC-04US3), in addition, the application also is involved in the common unsettled U.S. Patent application No.11/557 of the title of application on November 8th, 2006 for " Solid Oxide Fuel Cell Device and System; andMethod of Using and Method of Making ", 934 (attorney docket DEVOFC-04US4), more than respectively apply for disclosed content by with reference to and integrally be incorporated into this.
Technical field
The present invention relates to the manufacture method of fuel-cell device and system and this fuel-cell device, more specifically, relate to a kind of multilayer overall fuel cell rod TM(Fuel Cell Stick TM) fuel-cell device of form.
Background technology
Have been found that earthenware is applied to make Solid Oxide Fuel Cell (SOFC).Fuel cell has polytype, and every type has under incombustible situation and to transform fuel and air to produce the different mechanism of electric energy.In SOFC, the barrier layer between fuel and the air (" electrolyte ") is ceramic layer, and it can make oxygen atom move through this ceramic layer to finish chemical reaction.Because pottery at room temperature is a kind of non-conductor of oxygen atom, so operation of fuel cells is in 700 ℃ to 1000 ℃, and ceramic layer is done thinly as far as possible.
In early days, Westinghouse Electric (Westinghouse Corporation) uses long, the sizable zirconia ceramics extruded tube of diameter production tubular SOFC.Usually, length of tube is several feet long, and the diameter of pipe is 1/4 inch to 1/2 inch.The a whole set of structure of fuel cell generally includes about ten pipes.Development in time, researcher and industrial community have determined to contain the Y of 8mol% 2O 3The zirconia ceramics prescription.Except other production firm, this material is produced by the Tosoh of Japan, and product is TZ-8Y.
The another kind of method of making SOFC is to use the zirconia flat board, and this zirconia is dull and stereotyped to be stacked to form fuel cell structure with other anodes and negative electrode.Compare with the long and narrow device that Westinghouse Electric is expected, this slab construction can be cube shaped, and the length of side is 6 to 8 inches, and uses fixture that whole stacking material is kept together.
Another kind of newer method is to utilize the pipe that a large amount of diameters are less, wall is extremely thin.It is very important using the thin-walled pottery in SOFC, because the transmission rate of oxonium ion is subjected to the restriction of distance and temperature.If use thin zirconia layer, then the device of Xing Chenging can be operated under the lower temperature under the situation that keeps same efficiency.Described in the document and the wall thickness of earthenware need have been accomplished 150 μ m or littler.
Hinder the successful implementation of SOFC that several technical problem underlying are arranged.A problem is to prevent that ceramic component from ftractureing in heating process.For this reason, " piling up " formula scheme (being made by big and flat ceramic wafer) that the tubular SOFC scheme is better than competing with it is because pipe is one dimension substantially.For example, pipe can heat at the middle part, and expands but do not ftracture.For example, it is 36 that tube furnace can heat length ", diameter is 4 " alumina tube, and the middle part of alumina tube is heated to red heat, but the end is as cold as and can touches.Because pipe is evenly heated at middle part, this middle part expands, and makes pipe elongated, but does not ftracture.But ceramic wafer only can be broken into small pieces fast in the middle part heating, and side dimension remains unchanged because expand in the middle part.The key property of pipe is, it be single shaft to or one dimension.
Second significant challenge is to form with SOFC to contact.SOFC ideally is operated under the high temperature (usually 700-1000 ℃), but that it also needs to be connected to is extraneous obtaining air and fuel, and also needs to form and be electrically connected.Ideally, people wish at room temperature to connect.Owing to can not use organic material, it is problematic therefore at high temperature connecting, and it must use glass capsulation or mechanical seal.These sealings are insecure, and this part is because expansion issues.And their prices are also high.
Therefore, the difficulty of existing SOFC system relates to two problems recited above at least.In addition, the difficulty of plate technique also relates to the problem of panel edges at the gas ports seal aspect, and the problem of Fast Heating and cracking.The scheme of pipe has solved the cracking problem, but still has other problems.The SOFC pipe is only as gas container.In order to work, it must use in bigger air vessel.This is huger heaviness.Use the subject matter of pipe to be, must be with heat and air supply outside to pipe; Air provides O for reaction 2, heat is used for accelerated reaction.Usually, heat provides by combustion fuel, and what therefore provide is not to have 20%O 2In fact the air of (general value), air can partly reduce (partial combustion is to provide heat), and this can reduce the driving voltage of battery.
Also there is restriction in the quantity of SOFC pipe.In order to realize bigger kilovoltage output, must increase more pipe.Every pipe is independent dielectric substrate, thereby has obviously increased volume.Also there is restriction in the solid electrolyte Manifold technology aspect the electrolyte thinness that can realize.Electrolyte is thin more effective more.Be to obtain high power, best electrolyte thickness be 2 μ m or even 1 μ m, but this is very difficult to realize in solid electrolyte tube.It should be noted that single fuel cell zone produce about 0.5 to 1 volt voltage (identical with the mode of 1.2 volts of voltages of battery generation, this be because of the actuating force of chemical reaction intrinsic), but electric current and thus obtained power then depend on a plurality of factors.Higher electric current depend on make more oxonium ion preset time the Mobile Communication that moves to the interior cross electrolytical a plurality of factor.These factors comprise higher temperature, the electrolyte that approaches and bigger area.
Summary of the invention
The method that the present invention relates to fuel-cell device and system, uses the method for this device and system and make this device.According to one embodiment of the present invention, a kind of fuel-cell device comprises ceramic support structure, this ceramic support structure has reaction zone, and this reaction zone is configured to be heated to the working reaction temperature, and has first active layer and second active layer in this reaction zone.First active cell is arranged in described first active layer, this first active cell comprises the first anode, first negative electrode and first electrolyte between this first anode and first negative electrode, second active cell is arranged in described second active layer, and this second active cell comprises second plate, second negative electrode and second electrolyte between this second plate and second negative electrode.Has mutual electrical connector between a pair of identical electrode, wherein, this is the described first anode and second plate to identical electrodes or is described first negative electrode and second negative electrode, and wherein, this comprises parallel portion and bend to identical electrodes, and this parallel portion to identical electrodes is physically spaced apart, and this bend portion to identical electrodes physically electrically contacts, described bend forms described electrical connector, thereby with described first active cell and the second active cell parallel connection.A kind of fuel cell system also is provided, and this fuel cell system has the chamber, hot-zone, and the reaction zone of a plurality of described devices is arranged in the chamber, described hot-zone, and each cold-zone extends to the outside of chamber, described hot-zone.Thermal source is connected in chamber, described hot-zone, to be used for that described reaction zone is heated to described working reaction temperature, is provided with respectively the negative voltage connector and the positive voltage connector that contact with cathodic electricity with described anode in the described cold-zone.
In another embodiment, a kind of fuel-cell device comprises ceramic support structure, and this ceramic support structure has reaction zone, and this reaction zone is configured to be heated to the working reaction temperature, and has first active layer at least in this reaction zone.Have first active cell in described first active layer, this first active cell comprises first negative electrode and the first anode, and this first anode comprises the first atresia anode part and the first porous anode part relative with described first negative electrode.Also has second active cell in described first active layer, this second active cell is adjacent to described first active cell, and comprise that the second plate and second negative electrode, described second negative electrode comprise the second atresia cathode portion and the second porous cathode part relative with described second plate.Be provided with ceramic electrolyte in described first active layer, this ceramic electrolyte is between the described first anode and described first negative electrode and between described second plate and described second negative electrode.The described first atresia anode part is electrically connected in described ceramic support structure with the described second atresia cathode portion, thereby described first active cell and described second active cell are connected in described first active layer.A kind of fuel cell system also is provided, and as mentioned above, this fuel cell system comprises the device in a plurality of these execution modes.
In another embodiment, a kind of fuel-cell device comprises ceramic support structure, and this ceramic support structure has reaction zone, and this reaction zone is configured to be heated to the working reaction temperature, and has first active layer at least in this reaction zone.Described first active layer comprises ceramic electrolyte layer, be positioned at a plurality of isolated first electrode of first side of described ceramic electrolyte layer, and a plurality of isolated second electrode that is positioned at second side of described ceramic electrolyte layer, wherein, the polarity of described first electrode is opposite with the polarity of described second electrode, be chosen as male or female respectively, and wherein, in in described a plurality of isolated first electrode each and described a plurality of isolated second electrodes corresponding one relative, and described ceramic electrolyte layer is between relative this first electrode and second electrode.First electrode that each is relative and second electrode form active cell, thereby are distributed with a plurality of isolated active cells on described first active layer.Between described a plurality of isolated active cells, be extended with a plurality of electric-conductors, in wherein said a plurality of electric-conductor each contacts with the first electrode physics of an active cell, and extend through with the contiguous space of this active cell in described ceramic electrolyte layer, and contact with the second electrode physics of the active cell of adjacent spaces, thereby described a plurality of active cells are connected in described first active layer.A kind of fuel cell system also is provided, and as mentioned above, this fuel cell system comprises the device in a plurality of these execution modes.
In another embodiment of the invention, a kind of fuel-cell device comprises ceramic support structure, and this ceramic support structure has header field and bottom part, and has reaction zone, and this reaction zone is configured to be heated to the working reaction temperature.This device also comprises continuous active layer, this continuous active layer comprises first electrode layer, this first electrode layer is separated with opposite polarity the second electrode lay mutually by ceramic electrolyte layer, and extend to second end from first end with the zigzag form, described first end is connected on the described header field or is positioned near the described header field, described second end is connected described bottom and partly goes up or be positioned near the described bottom part, and the mid portion between described first end and second end comprises the active cell part between first bend and second bend.First gas passage is between active cell part and adjacent with described first electrode layer, second gas passage is between active cell part and adjacent with described the second electrode lay, wherein, at least one in described first bend or described second bend not with described header field and described bottom part between ceramic support structure be connected.
In another execution mode, a kind of fuel-cell device comprises ceramic support structure, has at least one active layer in this ceramic support structure, and be configured in chamber with reaction temperature work, wherein said at least one active layer comprises electrolyte between anode, negative electrode, described anode and the negative electrode, the fuel channel adjacent with described anode and the oxidant channel adjacent with described negative electrode.Be provided with at least one elongated ceramic end pipe, this at least one elongated ceramic end pipe has cold junction and hot junction, it is outer so that to be lower than the temperature work of described reaction temperature that described cold junction is configured to be positioned at chamber, described hot junction for good and all is connected in the end of described ceramic support structure, described ceramic end pipe is configured to supply a gas to the one or both in described fuel channel and the oxidant channel, and described ceramic end pipe has maximum sized length, so that thermal coefficient of expansion only has and the common main shaft that extends of described length.The combination of one or the following method of described ceramic end pipe in by the following method and for good and all be connected in described ceramic support structure: co-sintered under green state with described at least one elongated ceramic end pipe and described ceramic support structure, described at least one elongated ceramic end pipe of green state is sintered on the described ceramic support structure of sintering state, the described ceramic support structure of green state is sintered on described at least one elongated ceramic end pipe of sintering state, perhaps between the described ceramic support structure of described at least one elongated ceramic end Guan Yuyi sintering state of sintering state, applies glass bond or glass ceramics bonding agent and this described bonding agent between the two of sintering.
In another embodiment, a kind of fuel-cell device comprises elongated ceramic flat tube, the width of this elongated ceramic flat tube is greater than height, and between first end and second end, be extended with a plurality of fuel passage and a plurality of oxidant path along direction of elongate, this path is separated by the rib of inside, and is configured to prevent that fuel and oxidant from mixing between path.The multilayer active structure is connected on the plane of described elongated ceramic flat tube, this multilayer active structure comprises at least two active layers, each active layer comprises at least one active cell, this active cell has anode, negative electrode, electrolyte between described anode and the negative electrode, fuel channel adjacent and the oxidant channel adjacent with described negative electrode with described anode, wherein the described fuel channel fluid of each active cell is communicated in a plurality of fuel passage of described elongated ceramic flat tube one, and wherein the described oxidant channel fluid of each active cell is communicated in a plurality of oxidant paths of described elongated ceramic flat tube one, thereby fuel gas and oxidant gas are configured to be provided to respectively described fuel passage and oxidant path, enter described fuel channel and oxidant channel then respectively.
In another embodiment, a kind of fuel-cell device comprises multilayer active cell structure, this multilayer active cell structure has: a plurality of anode layers that alternately pile up with a plurality of cathode layers, comprise a plurality of first microtubules and/or nanotube channel in each described anode layer, each described cathode layer comprises a plurality of second microtubules and/or nanotube channel; And the dielectric substrate that separates of the cathode layer that each anode layer and each are replaced, thereby described anode layer in the inside of described multilayer active cell structure and cathode layer are used for two adjacent dielectric substrates separately.
In another embodiment, a kind of fuel-cell device comprises ceramic support structure, this ceramic support structure comprises multilayer active cell structure, this multilayer active cell structure has a plurality of anode layers, a plurality of cathode layers, the dielectric substrate that each anode layer is separated with each cathode layer, the active fuel passage that forms as one with each anode layer, and the active oxidizer passage that forms as one with each cathode layer, described ceramic support structure also has outward extending first elongate articles in an edge and second elongate articles from described multilayer active cell structure, described first elongate articles has the fuel feed passage that is connected in described active fuel passage, and described second elongate articles has the oxidant service duct that is connected in described active oxidizer passage.A kind of fuel cell system also is provided, and this fuel cell system has the chamber, hot-zone, and this chamber, hot-zone has chamber wall; And it is indoor that described multilayer active cell structure is arranged on described hot-zone, and described first elongate articles and described second elongate articles extend through described chamber wall and extend to described hot-zone outdoor.A plurality of stabilizing members extend in the described chamber wall from the described ceramic support structure around described multilayer active cell structure, thermal source is connected to chamber, described hot-zone, and is suitable for being heated to the working reaction temperature with being positioned at the indoor described multilayer active cell structure in described hot-zone.
Description of drawings
Comprise in this manual and constitute its a part of accompanying drawing showing embodiments of the present invention, and be used from explanation the present invention with describe, in general terms of the present invention that provides above and detailed description given below.
Fig. 1 and Figure 1A show the basic fuel cell rod of the present invention with sectional view and vertical view cutaway drawing respectively TM(Fuel Cell Stick TM) device a kind of execution mode, this execution mode has single anode layer, cathode layer and dielectric substrate and the hot-zone between cold-zone, two ends;
Fig. 2 shows fuel cell rod of the present invention with perspective view TMFirst end that is connected with fuel supply pipe of a kind of execution mode of device;
Fig. 3 A shows fuel cell rod according to one embodiment of the present invention with perspective view TMDevice, it has improved end;
Fig. 3 B shows the fuel supply pipe of an improved end of the device that is connected to Fig. 3 A with perspective view;
Fig. 4 A with perspective view show according to one embodiment of the present invention be used for form a plurality of fuel cell rods that are electrically connected with positive voltage node and negative voltage node TMThe metallurgical binding syndeton of device;
Fig. 4 B shows a plurality of fuel cell rods according to one embodiment of the present invention with schematic end view TMConnection between the device, wherein each fuel cell rod TMDevice comprises a plurality of anodes and negative electrode;
Fig. 5 with schematic end view show according to one embodiment of the present invention, be used for forming the mechanical connecting structure that is electrically connected with positive voltage node and negative voltage node;
Fig. 6 A and Fig. 6 B show optional execution mode with perspective view, wherein, and the fuel cell rod TMAn end that is connected with fuel and air supply pipe of device has single cold-zone, and the other end is in the hot-zone;
Fig. 7 A and Fig. 7 B show according to air of one embodiment of the present invention and a plurality of support columns in the fuel channel with sectional view and vertical view cutaway drawing respectively;
Fig. 7 C and Fig. 7 D show the micrograph according to the spheroid that is used as support column in fuel and air duct of another embodiment of the invention; Fig. 8 A shows according to one embodiment of the present invention with cutaway view, comprising two fuel cells of parallel connection outside;
Fig. 8 B shows the another embodiment of the invention that is similar to Fig. 8 A with cutaway view, but two fuel cells are in the parallel connection of inner utilization path;
Fig. 9 A and Fig. 9 B show multiple fuel cell design according to shared anode of having of one embodiment of the present invention and negative electrode with cutaway view, and wherein Fig. 9 A shows three fuel battery layers in parallel, and Fig. 9 B shows three fuel cells of series connection;
Figure 10 has gone out fuel cell rod according to one embodiment of the present invention with schematic side illustration TMDevice, wherein, fuel supply pipe is connected to the cold junction of device, installs a side and in the hot-zone air duct is opened, to be used for that hot-air is fed to device in the hot-zone;
Figure 10 A has gone out a kind of modification of the execution mode of Figure 10 with schematic side illustration, wherein, the hot-zone is between relative cold junction;
Figure 10 B shows the fuel cell rod of Figure 10 A TMInstall the vertical view cutaway drawing that 10B-10B along the line does;
Figure 11 to Figure 24 schematically shows different execution mode of the present invention, and wherein, Figure 11 provides the index of the various piece shown in Figure 12 to 24;
Figure 25 A to Figure 27 A has gone out the fuel cell rod with petioliform design according to one embodiment of the present invention with schematic plan and Figure 27 B with schematic side illustration TMDevice, wherein, elongate area is positioned at a cold end place, and the high surface area district is positioned at relative hot junction portion place;
Figure 25 B and Figure 26 A have gone out the optional execution mode of petioliform design with schematic plan and Figure 26 B with schematic side illustration, and wherein, two elongate area are positioned at relative cold end, and high surface area district in middle part is arranged in the hot-zone, middle part;
Figure 28 A to Figure 28 D shows the fuel cell rod with tubular structure spiral or that reel according to one embodiment of the present invention of the present invention TMDevice, wherein, Figure 28 A to Figure 28 C shows unwound structure with schematic plan, end view and end view respectively, and Figure 28 D illustrates tubular structure spiral or that reel with schematic perspective;
Figure 29 A to Figure 29 G shows another optional execution mode of the present invention, wherein, and the fuel cell rod TMDevice has the tubulose concentric structure, and Figure 29 A illustrates this device with the survey optical axis such as schematic, and Figure 29 B to Figure 29 E shows the cutaway view of Figure 29 A, and Figure 29 F shows the end view of air input, and Figure 29 G shows the end view of fuel input;
Figure 30 A shows fuel cell rod of the present invention with side schematic sectional view TMA kind of execution mode of device wherein had integrated preheating zone before the active region of hot-zone, Figure 30 B and Figure 30 C are the device schematic cross sectional views that 30B-30B and 30C-30C along the line did respectively of Figure 30 A;
Figure 31 A to Figure 31 C is similar to Figure 30 A to Figure 30 C, but shows two cold-zones and hot-zone, middle part;
Figure 32 A to Figure 32 B is respectively the side schematic sectional view done of the line 32B-32B along Figure 32 A and schematic vertical view cutaway drawing, show and the similar a kind of execution mode shown in Figure 31 A to Figure 31 C, but it also is included in the preheating chamber that extends and extend between fuel inlet and the fuel channel between air intake and air duct, each preheating chamber extends to the preheating zone of hot-zone from the cold-zone;
Figure 33 A to Figure 33 C shows and is used for another embodiment of the invention that air and fuel are carried out preheating, and wherein, Figure 33 A is through the fuel cell rod TMThe side schematic sectional view of longitudinal middle part of device, Figure 33 B is the schematic vertical view cutaway drawing that the line 33B-33B along Figure 33 A is done, Figure 33 C is the schematic upwarding cutaway view that the line 33C-33C along Figure 33 A is done;
Figure 34 A and 34B have gone out one embodiment of the present invention with schematically preceding oblique view and schematic side illustration respectively, and it has externally a plurality of anodes and the negative electrode of series connection mutually;
Figure 35 has gone out two structures of Figure 34 B with schematic side illustration, and these two structures externally connect by metal band, to form the series-multiple connection design;
Figure 36 A and 36B show another embodiment of the invention with schematic side elevation and perspective view, be included in the metal tape and the long metal tape of be used in the hot-zone to connect and/or be connected in parallel anode and negative electrode, described long metal tape extends to the cold-zone from the hot-zone, is used for forming the low temperature that is connected to the positive and negative voltage node in the cold-zone and connects;
Figure 37 shows and the similar a kind of execution mode of the execution mode of Figure 36 B with schematic isometric view, but it has single cold-zone, and described single cold-zone is used for that air is connected with the supply of fuel part and voltage node connects;
Figure 38 A and 38B show one embodiment of the present invention with side schematic sectional view, and it has along a plurality of delivery spaces of the side of device, so that with the organic material burn off that is used to form passage in the structure;
Figure 39 shows another embodiment of the invention with schematic cross-sectional end view, and wherein, anode material is called the fuel cell rod as supporting construction TMThe anode-supported pattern of device;
Figure 40 A and Figure 40 B show according to fuel cell rod of the present invention with schematic cross-sectional end view and side schematic sectional view respectively TMThe anode-supported pattern of the another kind of execution mode of device wherein, is utilized porous anode to play the function of transfer the fuel through device, thereby is no longer needed open fuel channel;
Figure 41 A and Figure 41 B show the fuel cell rod according to the present invention with schematic cross-sectional end view and schematic vertical view cutaway drawing respectively TMThe another kind of execution mode of the anode-supported pattern of device, wherein, a plurality of air ducts are located in the anode support structure, and single fuel channel is perpendicular to a plurality of air duct settings;
Figure 42 A to 42C shows the fuel cell rod of the present invention that is used for according to a kind of execution mode with schematic cross sectional views TMForm the method for electrode layer in the passage of device;
Figure 43 shows another embodiment of the invention with side schematic sectional view, and wherein, dielectric substrate is provided with uneven pattern, to be used to increase the surface area of collecting electrode layer;
Figure 44 shows the optional execution mode that is used for providing uneven pattern on dielectric substrate of the present invention with side schematic sectional view;
Figure 45 A shows fuel cell rod of the present invention with schematic plan view and Figure 45 B with the cutaway view by the hot-zone TMA kind of execution mode of device, this execution mode all has a plurality of fuel cells at the left and right side of device, has bridging part between the left and right side;
Figure 46 A and Figure 46 B show fuel cell rod of the present invention with perspective schematic view and schematic cross sectional views TMThe another kind of execution mode of device, this execution mode has big outside contact mat, makes the cold end of electrical conductivity auto levelizer so that big or wide low resistance path is provided;
Figure 47 shows the fuel cell rod of another embodiment of the invention with side schematic sectional view TMDevice, it has the fuel that is used to consume and the single discharge-channel of air;
Figure 48 A to Figure 48 C shows and is called " end coiling fuel cell rod TMDevice " optional execution mode, it has thickness portion and thin winding part, wherein, Figure 48 A shows unwound device with perspective view, Figure 48 B shows the device of coiling with sectional view, Figure 48 C shows the device of coiling with perspective view.
Figure 49 A shows the lead that uses between two ceramic layers with side schematic sectional view and makes up the fuel cell rod TMA kind of execution mode of device;
Figure 49 B illustrates the device shown in Figure 49 A behind the lamination with schematic perspective;
Figure 49 C illustrates the device shown in Figure 49 B that removes behind the lead with schematic perspective;
Figure 50 A to Figure 50 C shows the combination of using lead and gap to form band with schematic cross sectional views and makes up the fuel cell rod TMThe another kind of execution mode of device;
Figure 51 and Figure 52 A illustrate the fuel cell rod that passes the furnace wall with schematic perspective TMDevice;
Figure 52 B illustrates the fuel cell rod that is positioned at the furnace wall scope with schematic perspective TMThe device part;
Figure 52 C illustrates and will pass the tubular fuel cell rod of furnace wall with schematic perspective TMThe device part;
Figure 53 illustrates the fuel cell rod that passes the furnace wall that is made of multilayer with schematic perspective TMDevice;
Figure 54 illustrates the fuel cell rod of the furnace wall of passing multilayer and air gap formation with schematic perspective TMDevice;
Figure 55 A to Figure 55 E shows the fuel cell rod with suspension current-collector with schematic cross sectional views TMDevice assembly;
Figure 56 A and Figure 56 B are the micrographs that shows the zirconia ball that is used for the support suspension current-collector;
Figure 57 A and Figure 57 B show with being suspended in anode particle in the viscous liquid or the structure shown in cathode particles backfill Figure 55 D to form male or female with schematic cross sectional views;
Figure 58 A, Figure 58 B and Figure 58 C are the micrographs that shows the current-collector of basic blocking channel;
Figure 59 shows current-collector on anode and cathode surface with schematic cross sectional views;
Figure 60 shows the current-collector that is embedded in anode and the cathode surface with schematic cross sectional views;
Figure 61 A to Figure 61 C shows the current-collector landfill is located at method in the male or female;
Figure 62 shows the method that realization has the individual layer of two thickness with schematic cross sectional views;
Figure 62 A is the detail view of Figure 62;
Figure 63 is the microgram of overlooking that shows current-collector with hatching pattern;
Figure 64 and Figure 65 show the end view of the current-collector on porous anode or the negative electrode and the microgram of stravismus cutaway view;
Figure 66 A is slidingly mounted on the fuel cell rod TMThe schematic cross sectional views of the pipe of device end;
Figure 66 B is the fuel cell rod shown in Figure 66 A TMThe perspective schematic view of the end of device;
Figure 67 A is positioned at the fuel cell rod TMThe schematic cross sectional views of the connector that comprises the spring electric contact unit of device end;
Figure 67 B is the perspective schematic view of the connector of Figure 67 A;
Figure 68 A and Figure 68 B show the fuel cell rod with four outlets TMThe perspective schematic view of device;
Figure 69 is the micrograph that shows the current-collector person's movements and expression in recessed porous anode or the negative electrode;
Figure 70 is the micrograph of leaving gap behind demonstration removal carbon-wax expendable material;
Figure 71 has shown according to the path between a kind of two electrodes of execution mode with schematic cross sectional views and has connected;
Figure 72 has shown two interconnective electrodes according to a kind of execution mode with schematic cross sectional views;
Figure 73 A and Figure 73 B with perspective view and schematic cross sectional views show according to another kind of execution mode with two interconnective methods of electrode;
Figure 74 A to Figure 74 D has shown a kind of execution mode that uses bridging method to connect with schematic cross sectional views between battery;
Figure 75 A to Figure 75 E shows to use with perspective view and schematic cross sectional views and inserts the conductor method realizes the method for series connection between battery another kind of execution mode;
Figure 76 illustrates the another kind of execution mode that uses a plurality of insertion conductors to connect with schematic perspective;
Figure 77 shows a plurality of batteries of connecting according to any execution mode shown in Figure 75 A to Figure 76 with cutaway view;
Figure 78 A to Figure 78 C illustrates a kind of modification of inserting the conductor method with schematic perspective;
Figure 79 A to Figure 79 D shows the execution mode that uses path to connect with schematic cross sectional views and perspective view;
Figure 80 to Figure 81 shows a kind of execution mode of the Multi-layer Parallel in the individual layer series connection with schematic cross sectional views and explanatory view;
Figure 82 has shown the single layer fuel Battery Baton that is combined with the cascaded structure shown in Figure 74 C with schematic cross sectional views TMDevice;
Figure 83 A to Figure 83 B schematically shows the execution mode of the series-multiple connection combination of Figure 82 shown device;
Figure 84 A and Figure 84 B have shown the another kind of execution mode that is used for carrying out parallel connection between two electrodes at same gas path with perspective schematic view and schematic cross sectional views;
Figure 85 A and Figure 85 B have shown that with perspective schematic view the spiral with series design twines the tubular fuel cell rod of multilayer TMThe execution mode of device;
Figure 86 A and Figure 86 B have shown that with perspective schematic view spiral twines multilayer tubular fuel cell rod TMThe another kind of execution mode of device;
Figure 87 A and Figure 87 B are the exemplary details cutaway views of the execution mode of Figure 86 A and Figure 86 B;
Figure 88 A and Figure 88 B illustrate with schematic perspective and are used at the tubular fuel cell rod TMThe execution mode of electrical connection is provided in the device;
Figure 89 illustrates the layout of gas flow path with schematic perspective;
Figure 90 is to use the schematic diagram of the series-connected cell of folding path;
Figure 91 to Figure 92 B shows the fuel cell rod with multilayer series connection that uses the folded stack design with perspective schematic view and cutaway view TMThe execution mode of device;
Figure 93 A has shown that schematically to analyse and observe detail view being used to be connected folded stack designs so that the execution mode in the zone that freely suspends to be provided with Figure 93 B;
The parallel active layer that Figure 94 A to Figure 94 D shows the side that is connected to described device and freely suspends at the opposite side of this device with cross-sectional end view and vertical view cutaway drawing;
Figure 95 to Figure 97 shows two negative electrodes of series connection with schematic cross sectional views, is connected with the barrier layer between these two negative electrodes;
Figure 98 A illustrates the execution mode that electric power is connected with Figure 98 B with cutaway view and schematic perspective;
Figure 99 shows with schematic cross sectional views and is used for the execution mode that low resistance connects;
Figure 100 A to Figure 103 B illustrates the various execution modes of the fuel-cell device of the end pipe connections with permanent connection with schematic perspective;
Figure 104 illustrates the various ways of the ceramic core of presintering with schematic perspective;
Figure 105 A and Figure 105 B illustrate the flat tube with strutting piece and path with schematic perspective;
Figure 106 shows the flat tube of using in the method for prior art with schematic cross sectional views;
Figure 107 A, Figure 107 B and Figure 108 illustrate the application of flat tube path according to the embodiment of the present invention with partial perspective;
Figure 109 and Figure 110 show the execution mode of the distribution of gas of each layer from flat tube to the multilayer active structure with schematic cross sectional views;
Figure 111 illustrates the execution mode that flat tube is connected the outside, hot-zone with schematic perspective;
Figure 112 illustrates with schematic perspective flat tube is connected execution mode in the hot-zone;
Figure 113 illustrates the execution mode that flat tube is carried out the transition to the outside, hot-zone with schematic perspective;
Figure 114 illustrates the execution mode of the independent pipe in the flat tube that is used to be connected to the hot-zone with schematic perspective;
Figure 115 A is the micrograph of 500 times of amplifications that is used to form the fiber of microtubule;
Figure 115 B is the micrograph of 200 times of amplifications that is used to form the fiber of microtubule;
Figure 116 A to Figure 116 C is the micrograph that shows the microtubule in the electrode be formed on behind the sintering;
Figure 117 and Figure 118 are the exemplary details cutaway views that has the execution mode of the gas flow path that the electrode of microtubule intersects with inside;
Figure 119 is the schematic vertical view cutaway drawing of series design, and wherein gas stream passes electrode and enters other gas passage;
Figure 120 is the small fuel cell rod TMThe end view of the execution mode of device;
Figure 121 A and Figure 121 B show fuel cell rod shown in Figure 120 with vertical view and perspective view TMThe execution mode of device;
Figure 122 is the fuel cell rod shown in Figure 120 TMThe schematic side elevation of device wherein has point of safes on this device.
Below with reference to the accompanying drawings, wherein identical Reference numeral is represented identical parts in the text.Reference numeral used among the figure is as follows:
10 fuel cell rods TMDevice
11a first end
11b second end
12 fuel inlets
Preheating of fuel chambers 13
14 fuel channels
16 fuel outlets
18 air intakes
19 air preheating chambers
20 air ducts
21 discharge-channels
22 air outlet slits
24 anode layers
25 anode parts that expose
26 cathode layers
27 cathode portion of exposing
28 dielectric substrates
29 potteries
30 cold-zones (or second humidity province)
31 transition regions
32 hot-zones (or the thermal treatment zone or first humidity province)
The 33a preheating zone
The 33b active region
34 supply of fuel parts
36 air supply spares
38 negative voltage nodes
40 positive voltage node
42 electric wires
44 contact mats
46 are welded to connect portion
48 spring clips
50 supply pipes
52 bandages
54 support columns
56 first paths
58 alternate paths
60 barrier coats
62 surface particles
64 texture table surface layers
66 anode suspension
70 openings
72 (a, b) organic material/sacrifice belts
80 left sides
82 right sides
84 bridge parts
90 bridgewares
92 leads (physics) structure
94 gaps form band
96 furnace walls
96 ' multilayer furnace wall
96 " have the multilayer furnace wall of air gap
98a, b, c insulator
100 fuel cell rods TMDevice
102 elongate area
104 high surface area districts
106 elongate area
120 air gaps
122 current-collectors
123 gaps
124 electrode particles
126 viscous fluids
128 interim matrixes
130 pottery bands
132 recesses
134 connectors
136 electric contacts
138 gas flow paths
140 O type circles
142 macropores (in the pottery band)
The porous zone of 144 electrodes
The aporate area of 146 electrodes
148 connector electrodes (conductor belt)
150 slits
152 first conductors
154 second conductors
156 rectangle paths
158a, 158b, 158c, 158d plunger (path place)
160 edge connecting portions
162 middle part connectors
164 holes (in the gap band)
166 independent batteries
167 common-use tunnels
168 mandrels
170a, 170b conducting end
172 folded stack (floded stack)
174 barrier layers
176 insulating barriers
178 LSM band
180 inner fuel paths
182 nickel conductors
184 end pipes
186 reel holds pipe
190 cylindrical end
192 stomidiums
194 rectangle ends
196 rectangular tubes
198 shape transition end pipes
200 helix fuel cell rods TMDevice
300 concentric tube-shaped fuel cell rods TMDevice
400 end coiling fuel cell rods TMDevice
402 thick portions
404 thin portions
500 fuel cell rods TMDevice
600 fuel cell rods TMDevice
610 plates
612 rectangular slabs
614 pipes
616 flat tubes
618 strutting pieces
620 vertical ribs
622 triangle ribs
624 paths
The 624a fuel passage
The 624b air flue
626 lids
628 via path
630 high temperature manifolds
632 narrow flat tubes
634 fibers
636 cloth
638 microtubules
642 separators
700 fuel cell rods TMDevice
The bar-shaped inlet of 702a, 702b
704 big zones
706 point of safes
708 ridges
710 bigger connectors
Embodiment
In one embodiment, the invention provides a kind of SOFC device and system, wherein, fuel port and air port are formed in the overall structure.In one embodiment, the SOFC device is a kind of slim-lined construction, is essentially a kind of flat relatively rod or sq.rd and (therefore, is called the fuel cell rod TMDevice), wherein, the length of SOFC device is obviously greater than width or thickness.The fuel cell rod TMDevice can have cold end, and the middle part is hot (portion＞400 ℃ are pined in the temperature of cold end＜300 ℃, and is general＞700 ℃).The slow thermal conductance of pottery can prevent to pine for portion and heat colder end fully.In addition, this cold end can make any heat that arrives this end scatter and disappear fast.The present invention includes following implementing measure: be used for connecting by making cold end, can more easily be connected to anode, negative electrode, fuel inlet and H2O, CO2 outlet and air intake and air outlet slit.Though the tubular fuel cell structure also can have cold end and pine for portion, prior art can not be brought into play this advantage of earthenware, and on the contrary, it places stove or hot-zone with whole pipe, connects thereby need carry out high temperature.Prior art is recognized complexity and the cost that the high temperature brazing (brazed) of fuel inlet connects, but does not expect the solution that the present invention provides.Fuel cell rod of the present invention TMDevice is long and thin, thereby has hot property advantage recited above, makes it in the middle part heating but still have cold end.This makes energy satisfied temperature requirement on its structure, and it is relatively easy to connect fuel, air and electrode.The fuel cell rod TMDevice is a kind of autonomous system basically, only needs to add heat, fuel and air in order to generate electricity.This structure Design can solve these things easily.
Fuel cell rod of the present invention TMDevice is a sandwich construction, and can utilize the manufacturing of multilayer co-sintered (co-fired) method, obtains other several advantages thus.At first, this device is whole, and this helps to make its structure firmly reasonable.The second, this device itself is fit to conventional manufacturing process in enormous quantities, the technology of using during for example the MLCC of condenser plate (multilayer co-sintered pottery) produces.(can believe that multi-layer capacitor production is the maximum application in batches of industrial ceramics, and this technology be proved to be suitable for producing in enormous quantities.The 3rd, at the dielectric substrate that in this structure, can realize under the condition that does not increase extra cost or complexity approaching.Utilize the MLCC method can reach the thick dielectric substrate of 2 μ m, but the electrolyte wall thickness of SOFC pipe is difficult to less than 60 μ m.Therefore, fuel cell rod of the present invention TMThe efficient of device can exceed about 30 times than SOFC pipe.At last, multi-layer fuel cell rod of the present invention TMIn the device each can have hundreds of or several thousand layers, and this provides maximum area and maximal density.
Consider the SOFC pipe and fuel cell rod of the present invention of prior art TMThe surface area of device.For example, consider diameter 0.25 " pipe and 0.25 " * 0.25 " the fuel cell rod TMDevice.For pipe, its girth is 3.14 * D or 0.785 ".For 0.25 " the fuel cell rod TMDevice, the available width of one deck is about 0.2 inch.Therefore, need about 4 layers to reach and a pipe area identical.The digital difference of in these data and the capacitor technology those is very big.The state of the art of Japan's multi-layer capacitor is 600 the 2 thick layers of μ m at present.1000 layers of product may appear in Japan soon aborning, are to make in the laboratory now.These chip capacitors of 600 layers only are 0.060 " (1500 μ m).This manufacturing technology is applied to fuel cell rod of the present invention TMThe device, electrolyte thickness be 2 μ m and air/fuel passage have the thick cathode/anode of corresponding 10 μ m 0.25 " device in, can produce 529 layers single assembly.This equates 132 pipes.In order to obtain more high power, the strategy of prior art is to increase more pipe, increases diameter, and/or increases length of tube, and this causes the structure of high power output very big.On the other hand, for obtaining more high power, the present invention is at single fuel cell rod TMIncrease more layer in the device, and/or in device, use thin layer or passage, thereby make the miniaturization of SOFC technology.In addition, advantage of the present invention is a square effect, just as capacitor.When dielectric substrate was made a half thickness, power doubled, and can be equipped with more layer this moment in device, thereby power doubles once more.
Another key feature of the present invention is that it connects each layer easily and increases the fuel cell rod in inside TMThe output voltage of device.Suppose 1 volt every layer, then utilize path that Floor 12 is linked together for one group, fuel cell rod of the present invention TMDevice can obtain 12 volts of outputs.Then, further connection can be connected in parallel a plurality of Floor 12s for one group, to obtain higher electric current.This can utilize the method for using in the present condenser plate technology to finish.Key difference is that the present invention has overcome soldering and complicated line that other technologies must be used.
Compared with prior art, the present invention also provides more kinds of electrodes to select.Precious metal can be applied to anode and negative electrode.Silver is more cheap, but for higher temperature, need contain the mixture of Pd, Pt or Au, and Pd may be cheapest in three kinds of materials.Inexpensive metallic conductor has been paid close attention in a lot of researchs.In fuel-side, made great efforts to attempt using nickel, but any exposure in oxygen will make this burning under the high temperature.Conductivity ceramics also is known, and can use in the present invention.In a word, the present invention can use the anode/cathode/electrolyte system of any kind of of energy sintering.
In one embodiment of the invention, following situation may occur: when the band of large-area 2 μ m was not supported and has air in its both sides, this layer meeting became frangible.Can expect in the gap, being provided with post.These posts look and a bit look like post in stalactite and the cave that stalagmite contacts.They equably and spaced apart thick and fast, for structure provides better intensity
In order to connect gas and air supply spare, can expect that end region temperature is lower than 300 ℃, for example be lower than 150 ℃, thereby high temperature flexible silicon sebific duct or latex rubber pipe for example can be used to be connected to the fuel cell rod TMDevice.These flexible pipes can stretch on the end of cover auto levelizer simply, thereby form sealing.These materials can obtain in standard McMaster catalogue.Silicones usually under 150 ℃ or higher temperature as the stove pad, and can not lose its performance.Many bar fuels Battery Baton TMA lot of silicone tubes of apparatus system or latex rubber pipe can utilize barb connector (barb connection) to be connected to described gas feed.
Anode material or cathode material, perhaps two electrode materials can be metal or alloy.The used metal and the alloy that are fit to of anode and negative electrode is that persons skilled in the art are known.Alternatively, one or two electrode material can be the green ceramics (promptly not burning pottery, green ceramic) of conduction, and this also is that persons skilled in the art are known.For example, anode material can be the metallic nickel that partially sinters that is coated with yttria-stabilized zirconia, and cathode material can be the lanthanum manganite of modification, and it has perovskite structure.
In another embodiment, one or two electrode material can be the composite material of green ceramics and conducting metal, and wherein the content of metal is enough to make composite material conductive.Usually, when metallic particles began to contact, ceramic matrix became conduction.Be enough to make the amount of metal of matrices of composite material conduction to depend primarily on the form of metallic particles.For example, general, the spherical powder metal is than the needed amount of metal height of sheet metal.In an illustrative embodiments, composite material comprises green ceramics matrix and the conducting metal particles that disperses the 40-90% in the green ceramics matrix.The green ceramics matrix can be identical or different with the used green ceramics material of dielectric substrate.
Comprise in the execution mode of pottery (i.e. Dao Dian green ceramics) or composite material at one or two electrode material, the used green ceramics material of green ceramics in the electrode material and electrolyte can contain crosslinkable organic binder bond, thereby in lamination process, pressure is enough to make the organic binder bond in each layer crosslinked and make polymer molecular chain link between each layer.
Term " zone ", " district " and " section " can use instead in the text, are used to represent the identical meaning.Similarly, term " passage ", " path " and " path " can be used instead in the text, and term " outlet " and " outlet " can be used instead in the text.
Fig. 1 and Figure 1A show the basic fuel cell rod of the present invention with the form of sectional view and vertical view cutaway drawing respectively TMA kind of execution mode of device 10, this fuel cell rod TMDevice has single layer anode layer 24, cathode layer 26 and dielectric substrate 28, and wherein this device is whole.The fuel cell rod TMDevice 10 comprises fuel inlet 12, fuel outlet 16 and the fuel channel between the two 14.Device 10 also comprises air intake 18, air outlet slit 22 and the air duct between the two 20.Fuel channel 14 is in relative and parallel relation with air duct 20, flows with relative through the direction of the air stream of air ducts 20 from air supply spare 36 from the fuel of supply of fuel part 34 through fuel channel 14.Dielectric substrate 28 is between fuel channel 14 and the air duct 20.Anode layer 24 is between fuel channel 14 and the dielectric substrate 28.Similarly, cathode layer 26 is between air duct 20 and the dielectric substrate 28.The fuel cell rod TMDevice 10 remainder comprises pottery 29, and pottery 29 can be and dielectric substrate 28 identical materials, perhaps can be the ceramic material different but compatible with dielectric substrate 28.Dielectric substrate 28 can be counted as the part pottery between the opposed area that is in anode 24 and negative electrode 26, and is shown in dotted line.In dielectric substrate 28, oxonium ion is delivered to fuel channel 14 from air duct 20.As shown in Figure 1, through air duct 20, and be ionized into 2O from the O2 of air supply spare 36 by cathode layer 26 -(dioxygen anion), 2O -Enter fuel channel 14 by dielectric substrate 28 and anode layer 24, this with from the fuel of supply of fuel part 34 hydrocarbon reaction for example, thereby at first form CO and H 2, then form H 2O and CO 2Though Fig. 1 shows and utilizes hydrocarbon to act as a fuel to react, the invention is not restricted to this.Normally used any kind fuel can be all to be applied to the present invention among the SOFC.Supply of fuel part 34 can be for example any hydrocarbon source or sources of hydrogen.The example of hydrocarbon fuels has methane (CH 4), propane (C 3H 8) and butane (C 4H 10).
In order to react, must be to the fuel cell rod TMDevice 10 heating.According to the present invention, the fuel cell rod TMThe length long enough of device 10 can be divided into this device and is positioned at the hot-zone 32 (or thermal treatment zone) at device middle part and is positioned at the two ends 11a of device 10 and the cold-zone 30 at 11b place.Between hot-zone 32 and cold-zone 30, has transition region 31.Hot-zone 32 is usually operated at more than 400 ℃.In the exemplary embodiment, temperature＞600 of hot-zone 32 work ℃, for example＞700 ℃.Cold-zone 30 is not exposed under the thermal source, and because fuel cell rod TMDevice 10 the length and the hot property advantage of ceramic material, heat are scattered and disappeared beyond 32 in the hot-zone, thus the temperature of cold-zone 30＜300 ℃.Can believe that 32 to be delivered to cold-zone 30 ends along ceramic length be slowly to heat from the hot-zone, and the ceramic material of heat outside hot-zone 32 to be delivered to the air be quickish.Therefore, most of heats of input hot-zone 32 were lost to (mainly in transition region) in the air before arriving cold-zone 30 ends.In exemplary embodiment of the invention, the temperature of cold-zone 30＜150 ℃.In another illustrative embodiments, cold-zone 30 is in room temperature.The temperature of transition region 31 is between the temperature of the working temperature of hot-zone 32 and cold-zone 30, and a large amount of heats produce and scatter and disappear in transition region 31.
Because main thermal coefficient of expansion (CTE) is along the fuel cell rod TMDevice 10 length, and roughly be one dimension thus, therefore, allow the Fast Heating at middle part and can not ftracture.In the exemplary embodiment, the width of the length ratio device of device 10 and thickness are at least 5 times greatly.In further illustrative embodiments, the length of device 10 is the width of device and at least 10 times of thickness.In illustrative embodiments further, the length of device 10 is the width of device and at least 15 times of thickness.In addition, in the exemplary embodiment, width provides bigger area thus greater than thickness.For example, width can be the twice at least of thickness.As a further example, 0.2 inch thick fuel cell rod TMDevice 10 can have 0.5 inch width.Be understandable that accompanying drawing represents not in scale, and only provide the universal of relative dimensions.
According to the present invention, with anode 24 (being anode layer) and negative electrode 26 (being cathode layer) be connected electrically in the fuel cell rod TMCarry out the cold-zone 30 of device 10.In an illustrative embodiments, anode 24 and negative electrode 26 all 30 expose at the fuel cell rod in the cold-zone TMDevice 10 outer surface is electrically connected allowing.Negative voltage node 38 via electric wire 42 be connected to for example expose anode part 25, positive voltage node 40 is connected to the cathode portion of for example exposing 27 via electric wire 42.Because fuel cell rod TMDevice 10 has cold-zone 30 at two ends 11a, the 11b place of device, therefore can carry out the low temperature rigid electric and connect, and this has clear superiority than the prior art that generally needs high-temp soldering method to be electrically connected.
Fig. 2 shows the fuel cell rod with perspective view TMThe first end 11a of device 10, supply pipe 50 are contained in this first end 11a and upward and with bandage 52 fix.Thereby, can be transported to fuel inlet 12 through supply pipe 50 from the fuel of supply of fuel part 34.Because the first end 11a is in cold-zone 30, can use the connection material of flexible plastic pipe or other low temperature types that supply of fuel part 34 is connected to fuel inlet 12.The present invention does not need to use high temperature brazing to carry out fuel and connects.
Fig. 3 A shows the fuel cell rod with perspective view TMDevice 10, this is similar to device shown in Figure 1, but has the improved first and second end 11a, 11b.End 11a, 11b have been processed to cylinder-shaped end, so that being connected of supply of fuel part 34 and air supply spare 36.Fig. 3 B shows supply pipe 50 with perspective view and is connected to the first end 11a, to be used for that fuel is transported to fuel inlet 12 from supply of fuel part 34.As an example, supply pipe 50 can be silicone tube or latex rubber pipe, thereby utilizes its elasticity and the first end 11a to form tight seal.Be understandable that the flexibility of supply pipe 50 and elasticity can form the fuel cell rod when being applied to be subject to the mobile device of vibration effect TMThe absorption of vibrations retainer of device.In the prior art, pipe or plate are the rigidity solderings, thereby if be applied to dynamic environment, then are easy to Cracking Failure.Therefore, supply pipe 50 has special advantages as the additional functionality of vibration isolator than prior art.
Please again referring to Fig. 3 A, at the fuel cell rod TMDevice 10 outer surface is provided with contact mat 44, with expose anode part 25 with expose cathode portion 27 contact.The material of contact mat 44 should conduct electricity, thereby voltage node 38,40 is electrically connected to corresponding anode 24 and negative electrode 26.Be understandable that, can use any suitable method to form contact mat 44.For example, metal gasket can be printed on the fuel cell rod of sintering TMOn the outer surface of device 10.Electric wire 42 for example is fixed on the contact mat 44 by the portion of being welded to connect 46, to form reliable connection.Scolder is a cryogenic material, owing to be in the fuel cell rod TMThe cold-zone 30 of device 10, so scolder can adopt cryogenic material.For example, can use 10Sn88Pb2Ag scolder commonly used.The present invention has eliminated and has carried out the needs that high temperature voltage connects, and uses any low temperature to connect material or method thereby can expand.
In the perspective view of Fig. 3 A, also show fuel outlet 16 and air outlet slit 22.Fuel enters by the fuel inlet 12 on the first end 11a that is in a cold-zone 30, by with the contiguous outlet 16 of the second end 11b from the fuel cell rod TMDischarge the side of device 10.The air intake 18 of the second end 11b of air by being arranged in cold-zone 30 enters, from the fuel cell rod TMAir outlet slit 22 with a side first end 11a vicinity device 10 is discharged.Though exporting 16 and 22 is expressed as and is in the fuel cell rod TMThe same side of device 10, but be understandable that they can be in the opposite flank, for example, shown in following Fig. 4 A.
By making air outlet slit 22 (similarly near fuel inlet 12, fuel outlet 16 is near air intake 18) and by making the closely close of overlapping layer (anode layer, cathode layer, dielectric substrate), air outlet slit 22 plays the function of heat exchanger, advantageously preheating through the fuel of fuel inlet 12 accesss to plant 10 (fuel outlet 16 preheatings enter air) similarly, through air intake 18.Heat exchanger has improved the efficient of system.Transition region has the air that consumed and the overlay region of fresh fuel (and the fuel that consumed and fresh air), makes and transmitted heat before fresh fuel (fresh air) arrives the hot-zone.Therefore, fuel cell rod of the present invention TMDevice 10 is the overall structures that comprise embedded heat exchanger.
Referring to Fig. 4 A, show a plurality of fuel cell rods with perspective view TMDevice 10 (is two fuel cell rods in this case TMDevice) connection, be by make be connected in expose each contact mat 44 alignment of anode part 25 and electric wire 42 welding (at Reference numeral 46 places) that will be connected to negative voltage node 38 realize to each contact mat 44.Similarly, be connected to expose the contact mat 44 of cathode portion 27 be aligned, and electric wire 42 welding (at Reference numeral 46 places) that will connect positive voltage node 40 to the contact mat 44 of each alignment, are represented as dotted portion.Be understandable that, be positioned at cold-zone 30 because connect, and be relatively simply to connect, therefore, change the multiple fuel cell rod if desired TMA fuel cell rod in system or the assembly TMDevice 10 then only needs to disconnect being welded to connect of a device 10, and this device is replaced by new equipment 10, again electric wire 42 is welded to the fresh fuel Battery Baton TMOn the contact mat 44 of device 10.
Fig. 4 B shows a plurality of fuel cell rods with end-view TMConnection between the device 10, wherein, each fuel cell rod TMDevice 10 comprises a plurality of anodes and negative electrode.For example, the embodiment shown in Fig. 4 B comprises three groups of relative anodes 24 and negative electrode 26, and each anode exposes at the fuel cell rod TMThe right side of device 10, each negative electrode exposes at the fuel cell rod TMThe left side of device 10.Therefore, contact mat 44 is arranged at the fuel cell rod TMDevice 10 both sides, with contact expose accordingly anode part 25 and expose cathode portion 27.On the right side, anode 24 expose the position, by the portion of being welded to connect 46 electric wire 42 is fixed on the contact mat 44, thus with negative voltage node 38 be connected to expose anode part 25 on.Similarly, electric wire 42 is fixed on the contact mat 44 by the portion of being welded to connect 46, thereby at the fuel cell rod TMInstall 10 left sides with positive voltage node 40 be electrically connected to expose cathode portion 27 on.Therefore, relative although Fig. 1 to Fig. 4 A shows an anode 24 with a negative electrode 26, be understandable that, shown in Fig. 4 B, each fuel cell rod TMDevice 10 can comprise a plurality of anodes 24 and negative electrode 26, and make that each anode 24 and negative electrode 26 expose to the fuel cell rod TMThe outer surface of device 10 is electrically connected so that utilize the contact mat 44 that is set to outer surface to form, to be used to be connected to correspondent voltage node 38 or 40.In this structure the quantity of relative anode 24 and negative electrode 26 can be tens, hundreds of even several thousand.
Fig. 5 shows with end-view and form the mechanical connecting structure that is electrically connected between electric wire 42 and contact mat 44.In this execution mode, the fuel cell rod TMDevice 10 is positioned such that one group of electrode is at the fuel cell rod TMThe end face of device 10 exposes.Contact mat 44 can be an end 30 places, cold-zone of (for example, 11a or 11b) be set on each end face.Then, can electric wire 42 be detachably fixed on the contact mat 44 with spring clip 48.Therefore, can use the metallurgical binding method to form and be electrically connected, for example shown in Fig. 3 A, Fig. 4 A and Fig. 4 B; Perhaps can use the mechanical connection method, as shown in Figure 5.Select the flexibility of suitable junctor method to have benefited from fuel cell rod of the present invention TMThe cold-zone 30 of device.Use spring clip or other mechanical connecting structure further to simplify the single fuel cell rod of changing in many rod assemblys TMThe process of device 10.
Fig. 6 A and Fig. 6 B show at the fuel cell rod with perspective view TMThe first end 11a place of device 10 has single cold-zone 30 and has a kind of selectable execution mode of hot-zone 32 at the second end 11b.In Fig. 6 A, the fuel cell rod TMDevice 10 comprises three fuel cells in parallel, and the fuel cell rod of Fig. 6 B TMDevice 10 comprises single fuel cell.Therefore, embodiments of the present invention can comprise the design of single battery or the design of a plurality of batteries.In order to utilize an end to import fuel and air simultaneously, air intake 18 is repositioned at the fuel cell rod TMInstall on 10 sides and and be close to the first end 11a.Air duct 20 (not shown) is still parallel with fuel channel 14, but in this execution mode, air flows is according to flowing through the fuel cell rod with fuel TMThe identical direction of direction of the length of device 10.At the second end 11b place of device 10, air outlet slit 22 is contiguous with fuel outlet 16.Be understandable that, fuel outlet 16 or air outlet slit 22, perhaps the two can be from the fuel cell rod TMInstall 10 sides and discharge, rather than all discharge at end face.
Shown in Fig. 6 B, the supply pipe 50 of air supply spare 36 forms as follows, promptly by formation pass air supply spare 36 supply pipe 50 the side the hole and will install 10 slips and pass the hole of this side, thereby make the supply pipe 50 of air supply spare 36 perpendicular to the supply pipe 50 of supply of fuel part 34.Moreover silicone tube or analog can be used for this execution mode.Binding material can be applied in pipe 50 and install around the joint between 10 to form sealing.Also can be adjacent to the first end 11a in cold-zone 30 is electrically connected.Fig. 6 A and Fig. 6 B all show positive voltage and are connected to form at the fuel cell rod TMOne side of device 10, and negative voltage is connected to form at the fuel cell rod TMThe opposite side of device 10.Yet, be understandable that the present invention is not limited to this.Single-ended input type fuel cell rod TMThe advantage of device 10 is, only has a cold and hot transition region, rather than two transition regions 31, thus the fuel cell rod TMDevice can shorten.
An advantage of the invention is and active layer can be done very thin, thereby make the fuel cell rod TMDevice can be combined in a plurality of fuel cells in the single assembly.Active layer is thin more, and air duct 20 or fuel channel 14 are at the fuel cell rod TMThe possibility of subsiding in the manufacture process of device 10 is just big more, thereby stops flowing through described passage.Therefore, in one embodiment of the invention, shown in Fig. 7 A and Fig. 7 B, provide a plurality of support columns 54 in passage 14 and 20, for example the ceramic support post blocks to prevent dielectric substrate distortion and passage.Fig. 7 A is a sectional view, and Fig. 7 B is the vertical view cutaway drawing that passes air duct 20.A method according to the present present invention by using band casting method (tape casting), can be used the sacrifice belt, for example forms a plurality of holes by laser ablation material method in sacrificing belt.Then ceramic material is filled in the hole, for example sacrifices on the belt to enter in these holes by ceramic slurry is laid on.After each layer fits together, for example sacrifice the expendable material of belt by removal of solvents, stay support column 54.
In the another kind of execution mode that forms support column 54, bulky grain presintering pottery can add in the organic carrier (for example being dissolved in the plastics in the solvent), and stirs the formation random mixture.And nonrestrictive, bulky grain can be spherical as an example, and for example diameter is 0.002 inch a ball.Then, random mixture is applied on the green structure, for example by form the zone printing of fuel and air duct 14 and 20 at needs.In sintering (roasting/fire) process, organic carrier breaks away from structure (for example, burning), thereby forms passage, and ceramic particle stays the structurally support column 54 to keep clear emergency exit of formation.The structure that obtains is illustrated in the micrograph of Fig. 7 C and Fig. 7 D.Support column 54 random position, average distance are the functions of the useful load of ceramic particle in the organic carrier.
Fig. 8 A shows the one embodiment of the present invention that contain two fuel cells in parallel with cutaway view.Each active electrolyte layer 28 has air duct 20 and cathode layer 26a or 26b that is positioned at a side and fuel channel 14 and anode layer 24a or the 24b that is positioned at opposite side.The air duct 20 of a fuel cell separates by the fuel channel 14 of ceramic material 29 with second fuel cell.Expose anode part 25 be connected to negative voltage node 38 by electric wire 42 respectively, the cathode portion of exposing 27 is connected to positive voltage node 40 by electric wire 42 respectively.Then, can use single air supply spare 36, use single supply of fuel part 34 to be each fuel supplying in a plurality of fuel channels 14 for each the supply air in a plurality of air ducts 20.The circuit table of being set up by the said structure of active layer is shown in the right side of figure.
In the cutaway view of Fig. 8 B, the fuel cell rod TMDevice 10 is similar to the device shown in Fig. 8 A, but does not have a plurality of anode parts that expose 25 and a plurality of cathode portion of exposing 27, but only exposes an anode layer 24a at Reference numeral 25 places, and only exposes a cathode layer 26a at Reference numeral 27 places.First path 56 connects cathode layer 26a and cathode layer 26b, and alternate path 58 connects anode layer 24a and anode layer 24b.As an example, use laser method to obtain the open passageway hole in forming the green layer process, the filled conductive material forms the path connection then.Shown in the circuit on Fig. 8 B right side, at the fuel cell rod of Fig. 8 B TMForm fuel cell rod in the device 10 with Fig. 8 A TMInstall 10 identical circuit.
Fig. 9 A and Fig. 9 B also show a plurality of fuel cell design with cutaway view, but have shared anode and negative electrode.In the execution mode of Fig. 9 A, the fuel cell rod TMDevice 10 comprises two fuel channels 14 and two air ducts 20, but is not two fuel cells, and this structure comprises three fuel cells.First fuel cell is formed between anode layer 24a and the cathode layer 26a, is dielectric substrate 28 in the middle of this anode layer 24a and the cathode layer 26a.Anode layer 24a is in a side of fuel channel 14, is second plate layer 24b at the opposite side of this fuel channel 14.Second plate layer 24b is relative with the second cathode layer 26b, is another dielectric substrate 28 between the two, thereby forms second fuel cell.The second cathode layer 26b is in a side of air duct 20, and the 3rd cathode layer 26c is at the opposite side of air duct 20.The 3rd cathode layer 26c is relative with third anode layer 24c, is dielectric substrate 28 between the two, thereby forms the 3rd fuel cell.Device 10 part from anode layer 24a to cathode layer 26c can repeat repeatedly in device forming common anode and negative electrode, thereby at single fuel cell rod TMQuantity of fuel cells is increased.Each anode layer 24a, 24b, 24c comprise the anode part 25 that exposes, and this anode part that exposes 25 can be at the fuel cell rod TMForm electrical connection on the outer surface of device, for example to be connected to negative voltage node 38 by electric wire 42.Similarly, each cathode layer 26a, 26b, 26c comprise the cathode portion of exposing 27 to outer surface, for example to be connected to positive voltage node 40 by electric wire 42.At a cold junction place single air supply spare 36 can be set, so that be each air duct 20 supply air; At relative cold end place single supply of fuel part 34 can be set, so that be each fuel channel 14 fuel supplying.The circuit table that this structure forms is shown in the right side of Fig. 9 A.The fuel cell rod TMDevice 10 has three fuel battery layers in parallel, can obtain three times power.For example, if each layer produces 1 volt and 1 peace, then the power of 1 watt of each fuel battery layer generation is exported (volt * peace=watt).Therefore, this three-decker will produce 1 volt and 3 peaces, 3 watts power output altogether.
In Fig. 9 B, the structure of Fig. 9 A is modified to provide with the single of each voltage node and is electrically connected, forming three fuel cells of series connection, shown in the circuit on the right side of Fig. 9 B.Positive voltage node 40 is connected to cathode layer 26a at cathode portion 27 places of exposing.Anode layer 24a is connected to cathode layer 26b by path 58.Anode layer 24b is connected to cathode layer 26c by path 56.Anode layer 24c and then be connected to negative voltage node 38 at the anode part 25 that exposes.Therefore, utilize the hypothesis of/1 volt of every layer 1 identical peace, this three batteries structure produces 3 volts and 1 peace, 3 watts power output altogether.
Another embodiment of the invention is illustrated in the end view of Figure 10.In this execution mode, the fuel cell rod TMDevice 10 has single cold-zone 30 at the first end 11a place, and the second end 11b is in the hot-zone 32.As other execution modes, fuel inlet 12 is in the first end 11a place, and is connected to supply of fuel part 34 by supply pipe 50.In this execution mode, fuel channel 14 is along the fuel cell rod TMThe length of device 10 is extended, and makes fuel outlet 16 be in the second end 11b place.Therefore, supply of fuel connects to be carried out in cold-zone 30, and the exit of fuel reactant (for example, CO2 and H2O) is in hot-zone 32.Similarly, anode has the anode part 25 that exposes in cold-zone 30, so that be connected to negative voltage node 38 by electric wire 42.
In execution mode shown in Figure 10, the fuel cell rod TMDevice 10 is open at least one side, also can all open at two opposite sides so that in the hot-zone 32 formation air intake 18 and air ducts 20.In this execution mode, in air duct 20, use support column 54 particularly useful.Air outlet slit 22 can be positioned at the second end 11b place, as shown in the figure.Alternatively, though not shown,, if passage 20 extends through width and air supply spare only towards input side, if perhaps passage 20 does not extend through width, then air outlet slit can be in the opposite side of air intake side.In this execution mode, not only to provide heat to hot-zone 32, air also is provided.In other words, device 10 32 side open to heated air in the hot-zone, rather than supplies air through the pressure air pipe.
Figure 10 A shows the modification of execution mode shown in Figure 10 with end view.In Figure 10 A, the fuel cell rod TMDevice 10 comprises relative cold-zone 30, and the thermal treatment zone, middle part 32 separates with cold-zone 30 by transition region 31.Air intake 18 is arranged at least a portion of the thermal treatment zone 32, middle part, is used to receive heated air.Yet, in this execution mode, air duct be not image pattern 10 the same on significantly big length at the fuel cell rod TMThe side of device 10 is unlimited fully.Relatively, more clearly shown in Figure 10 B, air duct 20 opens wide on a part of hot-zone 32, seals on the side of all the other length then, subsequently at the fuel cell rod TMAir outlet slit 22 places of the second end 11b of device 10 discharge.This execution mode allows heated air 32 supplies in the hot-zone, rather than the supply of depended on pressure air supply pipe, but also allows an end 11b of fuel and the air device 10 from be in cold-zone 30 to discharge.
Though detailed icon and described concrete execution mode, scope of the present invention is not limited thereto.More generally execution mode of the present invention will be described below, and them can be more fully understood with reference to figures 11 to schematic diagram shown in Figure 24.Figure 11 provides the legend index of the member of schematically representing among Figure 12 to Figure 24.At fuel F or air A to enter the fuel cell rod TMUnder the situation that the arrow of device is represented, this represents forced flow, for example by being connected to the pipe of position, input port.Import under the unshowned situation at air, the measure beyond this expression heated air connects by forced flow is fed to the hot-zone, and the fuel cell rod TMThe inlet point place of device in the hot-zone opens wide air duct.
One embodiment of the present invention are fuel cell rods TMDevice, described fuel cell rod TMDevice comprises at least one fuel channel and corresponding anode, at least one oxidant channel and corresponding negative electrode, and the electrolyte between anode and the negative electrode, wherein battery length is obviously greater than width or thickness, thereby have along the CTE of a main shaft, and the working temperature of the part of its hot-zone is greater than about 400 ℃.In this execution mode, the fuel cell rod TMDevice has the integrated form inlet point that is used for air and fuel input according to main CTE direction at the place, an end of device; Perhaps have air intake at place, end, and have fuel inlet, and air and fuel input are in outside the hot-zone at another place, end according to main CTE direction.For example, referring to Figure 20 and Figure 24.
In another embodiment of the invention, fuel cell has first humidity province and second humidity province, and wherein first humidity province is the hot-zone, and its working temperature is enough to carry out fuel cell reaction; Second humidity province is operated in than under the low lower temperature in first humidity province in the outside, hot-zone.The temperature of second humidity province is enough low, is connected and allows the low temperature connection of supply of fuel part at least to allow forming low temperature with electrode.Fuel cell structure partly stretches into first humidity province, and partly stretches into second humidity province.For example, referring to Figure 12, Figure 13 and Figure 17.
In one embodiment of the invention, fuel cell comprises first humidity province that is in the thermal treatment zone and is operated in second humidity province under the temperature below 300 ℃.Air is connected with fuel to connect as low temperature and utilizes rubber tube or analog to form in second humidity province.Soldered connecting portion or spring clip are used to form the electrical connection of anode and negative electrode, so that they are connected to corresponding negative voltage node and positive voltage node.In addition, be used for the fuel outlet of carbon dioxide and water and the air outlet slit of the oxygen that is used to consume is positioned at first humidity province, the i.e. thermal treatment zone.For example, referring to Figure 17.
In another embodiment, fuel cell structure has first humidity province, middle part as the thermal treatment zone, and the working temperature that each end of fuel cell is arranged in outside first humidity province is lower than 300 ℃ second humidity province.Fuel and air intake are in second humidity province, are used to be electrically connected to the portion that is welded to connect of anode and negative electrode or spring clip also in this district.At last, the outlet that is used for the oxygen of carbon dioxide, water and consumption can be in second humidity province.For example, referring to Figure 19, Figure 20 and Figure 24.
In another embodiment of the invention, fuel inlet can be arranged on according to the place, each end of main CTE direction, working temperature is lower than in 300 ℃ second humidity province, first humidity province is the thermal treatment zone, and is in the middle part between the second relative humidity province.The outlet of the oxygen of carbon dioxide, water and consumption can be in the thermal treatment zone, middle part.For example, referring to Figure 15 and Figure 18.Alternatively, the outlet of the oxygen of carbon dioxide, water and consumption can be in second humidity province, promptly outside the thermal treatment zone.For example, referring to Figure 16 and Figure 19.
In another embodiment, fuel and air intake inlet point all be in as outside first humidity province of the thermal treatment zone, working temperature is lower than in 300 ℃ second humidity province, thereby allow to use low temperature to connect, for example be used for the rubber tube of air and supply of fuel.In addition, in second humidity province, use and be welded to connect portion or spring clip, to be used for that voltage node is connected to anode and negative electrode.In one embodiment, fuel and air intake are all at the place, an end according to main CTE direction, fuel cell rod TMAnother end of device is in the first heating-up temperature district, and the outlet of the oxygen of carbon dioxide, water and consumption can be in the thermal treatment zone.For example, referring to Figure 17.Therefore, fuel cell rod TMDevice has not heated end portion of a heated end portion and.
In another embodiment, fuel and air are input to an end according to main CTE direction that is arranged in outside the thermal treatment zone, and also the opposed end place outside the thermal treatment zone discharges, thereby the thermal treatment zone is between two second relative humidity provinces.For example, referring to Figure 20.In another optional execution mode, fuel and air are input to two opposed ends in second humidity province, and fuel and air outlet slit are in the thermal treatment zone, middle part.For example, referring to Figure 18.
In another optional execution mode, fuel and air are input in two opposed ends that are in second humidity province, and corresponding outlet is in second humidity province at the place, end relative with inlet.For example, referring to Figure 19.Therefore, fuel cell has the thermal treatment zone, middle part and is positioned at opposed end outside the thermal treatment zone, and fuel and air are all imported first end, and corresponding product is adjacent to second end and discharges, and fuel and air are input to second end, and product is adjacent to first end and discharges.
In another embodiment, fuel inlet can be located an end outside the thermal treatment zone, and air intake can be located the relative end outside the thermal treatment zone.For example, referring to Figure 21 to Figure 24.In this execution mode, the reactant of air and fuel can be in the thermal treatment zone (referring to Figure 21) output, perhaps they can be outside the thermal treatment zone, and is adjacent to the end relative with corresponding inlet and locates (referring to Figure 24).Alternatively, carbon dioxide and water out can be in the hot-zones, and the oxygen outlet that consumed can be outside the hot-zone (referring to Figure 22), and be perhaps relative, the oxygen outlet that consumed can be in the thermal treatment zone, and carbon dioxide and water out are in (referring to Figure 23) outside the thermal treatment zone.The modification relevant with air outlet slit with fuel shown in Figure 23 with Figure 22 for example also can be applied to Figure 18 to execution mode shown in Figure 20.
In another embodiment of the invention, it is illustrated in the end view of the vertical view of Figure 25 A and Figure 27 A and Figure 27 B, the fuel cell rod that is provided TMDevice 100 has the structure that can be called the petioliform design.The fuel cell rod TMDevice 100 has elongate area 102, can be similar to the fuel cell rod shown in the execution mode of front on this elongate area size TMDevice, elongate area 102 has along the CTE of a main shaft, and promptly its length is obviously greater than width or thickness.The fuel cell rod TMDevice 100 also has high surface area district 104, and its width is more near its length.High surface area district 104 can be square surface area or rectangular surfaces zone, but the width in this rectangular surfaces zone is not to be significantly less than length, make CTE have single main shaft, but have along its length the CTE axis with Width.High surface area district 104 is arranged in hot-zone 32, and elongate area 102 to small part is arranged in cold-zone 30 and transition region 31.In an illustrative embodiments, a part of elongate area 102 extends in the hot-zone 32, but this not necessarily.As an example, fuel and air supply spare can be connected to elongate area 102 by the mode shown in Fig. 6 B, and it also is like this being electrically connected.
In the end view of the vertical view of Figure 25 B and Figure 26 A and Figure 26 B, provide another the optional execution mode shown in a kind of Figure 25 of being similar to A, Figure 27 A and Figure 27 B, but it also has second elongate area 106 relative with elongate area 102, thereby high surface area district 104 is positioned between two elongate area 102 and 106.Elongate area 106 also is in cold-zone 30 and the transition region 31 at least in part.In this execution mode, fuel can be imported elongate area 102, and air can be imported elongate area 106.As an example, this moment, air supply spare 36 and supply of fuel part 34 can correspondingly be connected to elongate area 106 and 102 respectively according to the mode shown in Fig. 2 or Fig. 3 B.Shown in Figure 25 B, air outlet slit can be close to the fuel input in elongate area 102, and fuel output can be adjacent to the air intake that is in the elongate area 106.Alternatively, one in air and the fuel output or the two can be in the high surface area district 104 of hot-zone 32, respectively shown in vertical view 26A and end view 26B.Be understandable that in the execution mode shown in Figure 25 A and the 25B, the centre has the relative anode 24 of electrolyte 28 and the surface area of negative electrode 26 can increase in hot-zone 32, so that the augmenting response zone, thereby the fuel cell rod increased TMThe power that device 100 produces.
Fuel cell rod of the present invention TMAnother advantage of device 10,100 is in light weight.Typical internal combustion engine weight is on the level of every kW power 18-30lbs (pound).Fuel cell rod of the present invention TMDevice 10,100 can accomplish that weight is on the level of the corresponding 0.5lbs of every kW power.Figure 28 A to Figure 28 D shows tubular fuel cell rod of the present invention TMThe optional execution mode of device 200, it has the tubular structure of spiral or coiling.Figure 28 A is that device 200 is in the not schematic plan of winding position.The not winding-structure of device 200 has first end 202 and second end 204 of equal length L, and this length L is corresponding to reeling or helix fuel cell rod TMThe length of device 200.Fuel inlet 12 and air intake 18 are expressed as to be in and are adjacent to first end 202 at opposite side.Fuel channel 14 and air duct 20 extend to second end 204 along the width of the not winding-structure of device 200, thereby fuel outlet 16 and air outlet slit 22 are in second end 204, in addition, shown in the schematic side elevation of the not winding-structure of the schematic end of the not winding-structure of the device among Figure 28 B 200 and the device 200 among Figure 28 C.Fuel channel 14 and air duct 20 are expressed as the length L of the not winding-structure that almost is extended with device 200, thereby make fuel and air flows maximization, but the present invention is not limited to this.In order to form helix fuel cell rod TMDevice 200, the first ends 202 are reeled with the spiral tube structure of the device 200 shown in the perspective schematic view that forms Figure 28 D towards second end 204.Then air supply spare 36 can be positioned at helix fuel cell rod TMThe place, end of device 200, being used for that air is input to air intake 18, and supply of fuel part 34 can be positioned at helix fuel cell rod TMThe opposed end of device 200 is to be used for that fuel is input to fuel inlet 12.Then, air and fuel are discharged helix fuel cell rod along the length L of device 200 through fuel outlet 16 and air outlet slit 22 TMDevice 200.Voltage node 38,40 can be soldered on the contact mat 44, and contact mat 44 is formed on helix fuel cell rod TMOn device 200 the relative end or be adjacent to relative end.
Figure 29 A to Figure 29 G shows optional execution mode of the present invention, wherein fuel cell rod TMDevice is the tubulose concentric shape.Figure 29 A surveys view with axle such as schematic and shows concentric tube-shaped fuel cell rod TMDevice 300.Figure 29 B to Figure 29 E shows the concentric device 300 of Figure 29 A with cutaway view.Figure 29 F shows the end-view of the air intake end of device 300, and Figure 29 G shows the end-view of the fuel inlet end of device 300.Illustrated special embodiment comprises 20, one middle parts that are in tubular structure of three air ducts, and other two are separated from each other and are concentric.Concentric tube-shaped fuel cell rod TMDevice 300 also has between air duct 20 and two fuel channels 14 concentric with air duct 20.Shown in Figure 29 A to Figure 29 D, concentric tube-shaped fuel cell rod TMDevice 300 comprises the fuel outlet 16 that is connected in fuel channel 14 at place, end, comprises the air outlet slit 22 that is connected in air duct 20 at the place, the other end relative with the corresponding inlet 12,18 of air duct.Each air duct 20 is lined with negative electrode 26, and each fuel channel 14 is lined with anode 24, and electrolyte 28 separates relative anode and negative electrode.Shown in Figure 29 A to Figure 29 B and Figure 29 F to Figure 29 G, can be at concentric tube-shaped fuel cell rod TMThe opposed end realization of device 300 is electrically connected with anode 25 that exposes and the negative electrode 27 that exposes.Contact mat 44 can be arranged on the end, with connection anode 25 that exposes and the negative electrode 27 that exposes, although not shown, contact mat 44 can extend along the outside of device 300, is electrically connected forming along some place of the length of device 300 rather than at the place, end so that allow.Concentric tube-shaped fuel cell rod TMDevice 300 can comprise the support column 54 that is positioned at air and fuel channel 14,20, to be used for support structure.
Have in the embodiments of the present invention of two cold-zones 30 at opposed end 11a, 11b, the place has air intake and fuel outlet an end, have fuel inlet and air outlet slit in relative end, used fuel or air are in heated condition when it flows out hot-zone 32, middle part.Heated air and fuel flow through at it and cool off when transition region 31 arrives cold-zone 30.Electrode and/or pottery/electrolytical thin layer separates air duct 20 with parallel fuel channel 14, vice versa.In a passage, heated air flows out hot-zone 32, and in contiguous parallel channels, fuel enters hot-zone 32, and vice versa.Utilize heat exchange principle, the fuel that enters that heated air will be close in the parallel channels heats, and vice versa.Therefore, make air and fuel obtain some preheatings by heat exchange.But because heat scatters and disappears fast outside the hot-zone, as mentioned above, heat exchange may be not enough to air and fuel were heated to best reaction temperature before it enters the active region of hot-zone.In addition, at the fuel cell rod TMDevice 10 comprises in the execution mode of a cold end (cold-zone 30) and a hot junction portion (hot-zone 32), fuel and the identical cold end of air input, and discharge by identical relatively hot end, thereby the cross flow one of the fuel and the air of heat exchange can not appear carrying out.By the fuel cell rod TMThe electrode and the ceramic material of device only can obtain the limited heat exchange that enters fuel and air.
Figure 30 A to Figure 33 C shows the fuel cell rod TMDevice 10 various different execution modes wherein, have integrated preheating zone 33a enter the active region 33b of the anode 24 that is in relativeness and negative electrode 26 at fuel and air before, to be used for heating fuel and air.These execution modes comprise: the fuel cell rod with two cold end and middle hot-zone TMDevice, wherein, fuel is positioned at relative cold end with air intake: and the fuel cell rod with a hot junction portion and a cold end TMDevice, wherein, fuel and air input are all in single cold end.In these execution modes, used electrode material amount can be limited to active region 33b, only has to extend to the cold-zone on a small quantity, is connected to voltage node 38,40 to be used for the outside.Another advantage of these execution modes is, electrical conductivity can be the shortest to the path that external voltage connects, thereby low resistance is provided, and this is more detailed description below.
Figure 30 A shows the fuel cell rod TMThe side schematic sectional view of first execution mode of device 10 wherein has a cold-zone 30 and a relative hot-zone 32 and integrated preheating zone 33a.Figure 30 B shows the cutaway view of upwards seeing towards air duct through anode 24, and Figure 30 C shows the cutaway view of observing towards fuel channel through negative electrode downwards.Shown in Figure 30 A and Figure 30 B, enter through fuel inlet 12 from the fuel of supply of fuel part 34, and flow through the length of fuel channel 14 along device 10, flow out fuel outlet 16 from installing 10 opposed end.Cold-zone 30 is in the fuel cell rod TMThe first end 11a place of device 10, hot-zone 32 is in second opposed end 11b place.Transition region 31 is between the hot and cold district.Hot-zone 32 comprise fuel at first process initial preheating zone 33a and comprise active region 33b with the contiguous anode 24 of fuel channel 14.Shown in Figure 30 B, the sectional area of anode 24 is bigger in the 33b of active region.Anode 24 extends to the fuel cell rod TMAn edge of device 10, outside contact mat 44 extends to cold-zone 30 along the outside of device 10, to be used to be connected to negative voltage node 38.
Similarly, shown in Figure 30 A and Figure 30 C, enter through the air intake 18 that is arranged in cold-zone 30 from the air of air supply spare 36, and by air duct 20 along the fuel cell rod TMThe length of device 10 flows, and then 32 process air outlet slits 22 are discharged from the hot-zone.Since air and fuel enter at place, same end and along equidirectional along the fuel cell rod TMThe length of device 10 is advanced, and therefore before hot-zone 32, by heat exchange air and fuel is carried out limited preheating.Negative electrode 26 is positioned at active region 33b, and itself and anode 24 are in relativeness, and extends to the fuel cell rod TMDevice 10 opposite side, that it exposes at this and be connected to the outside contact mat 44 that extends to cold-zone 30 from active hot-zone 33b, to be used to be connected to positive voltage node 40.Yet the negative electrode 27 that exposes is optional with the opposite side that the anode 25 that exposes is in device 10.Anode 25 that exposes and the negative electrode 27 that exposes can be in the same side of device, and contact mat 44 can be along the fuel cell rod TMThe side of device 10 forms band.Utilize this structure, air and fuel at first in preheating zone 33a heating, do not react herein, and the major part of anode material and cathode material is limited in active region 33b, be the position that heated air and fuel enter herein, and react owing to relative anode layer and cathode layer 24,26 at this.
Execution mode shown in Figure 31 A to Figure 31 C is similar to the execution mode shown in Figure 30 A to Figure 30 C, but does not have a hot junction portion and a cold end, and the execution mode shown in Figure 31 A to Figure 30 C comprises relative cold-zone 30 and hot-zone, middle part 32.Fuel inlet 12 through cold-zone 30 enters at the first end 11a place of device 10 from the fuel of supply of fuel part 34, and passes through fuel outlet 16 discharges that are positioned in the relative cold-zone 30 at second opposed end 11b place.Similarly, enter through air intakes 18 in cold-zone 30 relatively from the air of air supply spare 36, and discharge through air outlet slits 22 in first cold-zone 30.Fuel enters hot-zone 32 and in preheating zone 33a preheating, and 32 opposite side enters and in the 33a preheating of another preheating zone air in the hot-zone.Therefore, the cross flow one that has fuel and air.Anode 24 is relative with negative electrode 26 in the 33b of the active region of hot-zone 32, and reacts at the active region 33b that comprises pre-heating fuel and air.Moreover the major part of electrode material is limited in active region 33b.Anode is at the fuel cell rod TMAn edge of device 10 exposes, and negative electrode exposes at the opposite side of device 10.The anode 25 that exposes in the outside contact mat 44 contact hot-zones 32, and towards first cold end 11a extension, to be used to be connected to negative voltage node 38.Similarly, the negative electrode that exposes 27 in the outside contact mat 44 contact hot-zones 32, and towards second cold-zone 11b extension, to be used to be connected to positive voltage node 40.
The advantage of preheating zone 33a is before gas reaches the active region gas fully to be heated to optimal reaction temperature.If the temperature of fuel is lower than optimum temperature, then can reduce the efficient of SOFC system.When air and fuel were advanced on their paths, they were heated.Because they are heated, electrolytical efficient increases in this zone.When fuel, air and electrolyte reached the sufficient temperature of stove, electrolyte was worked under its optimum efficiency.In order to save the anode that to make by noble metal and the cost of negative electrode, can not use metal in those zones that still are lower than optimum temperature.The size of preheating zone aspect length and other sizes, depends on from stove to be delivered to the fuel cell rod TMThe device heat, from the fuel cell rod TMDevice is delivered to the heat of fuel and air and whether any heat exchange occurs owing to the cross flow one of fuel and air.Size also depends on the flow rate of fuel and air; If fuel or air are along the fuel cell rod TMInstall 10 length and flow fast, then long preheating zone 33a is favourable, and if flow rate is slow, then preheating zone 33a can be shorter.
Figure 32 A and Figure 32 B have illustrated shown in a kind of and Figure 31 A to Figure 31 C similarly execution mode, but the fuel cell rod TMDevice 10 comprises at fuel inlet 12 and extends to preheating chamber 13 between the fuel channel 14 of hot-zone 32, at preheating zone 33a these a large amount of fuel carried out preheating to be used for passing narrower fuel channel 14 at a large amount of fuel before entering active region 33b.The fuel cell rod TMDevice 10 comprises at air intake 18 similarly and extends to preheating chamber 19 between the air duct 20 of hot-zone 32, at preheating zone 33a these a large amount of air carried out preheating to be used for passing narrower air duct 20 at a large amount of air before entering active region 33b.As disclosed in the above-described embodiment, the fuel cell rod TMDevice 10 can comprise a plurality of fuel channels 14 and a plurality of air duct 20, and each fuel channel 14 and air duct 20 can receive fluid from preheating chamber 13,19 separately.
About using big capacity preheating chamber 13,19 to substitute preheating channel (pre-heat channel), can imagine (only as an example): if air molecule needed 5 seconds to be heated to optimum temperature, if air molecule is along the fuel cell rod then TM Device 10 speed with 1 inch of per second move, then fuel cell rod before air enters active region 33b TMIt is 5 inches preheating channel that device 10 needs length.But, if being set, big capacity chamber replaces passage, then this capacity allows molecule to spend the extra time in cavity entering narrower passage before arriving active region 33b, makes air molecule heat in described chamber and can use the short passage of length to supply to active region 33b with the air molecule that will heat then.Can form this cavity or preheating chamber 13,19 in several ways, comprise adopt green compact (green) (before being sintering) assembly and in the boring of the end of this assembly to form described chamber, perhaps by form green compact heap layers (green stack) before in this green compact heap layer in conjunction with the organic material of bulk, thereby make the roasting in sintering process of described organic material go out described fuel cell rod TMDevice.
Figure 33 A to Figure 33 C had shown before air and fuel arrive active region 33b another execution mode that air and fuel are carried out preheating.Figure 33 A passes through the fuel cell rod substantially TMThe cross-sectional schematic side view of the longitudinal center of device 10.Figure 33 B is the cross-sectional plan view of the line 33B-33B intercepting of intersecting along fuel channel 14 and anode 24, and Figure 33 C is the cross section upward view of the line 33C-33C intercepting of intersecting along air duct 20 and negative electrode 26.The fuel cell rod TMDevice 10 has two relative cold-zones 30 and hot-zone, middle part 32, has transition region 31 between each cooling 30 and the hot-zone 32.The fuel that provides from fuel supply part 34 enters the fuel cell rod by fuel inlet 12 TMThe first end 11a of device 10 also passes fuel channel 14 and moves, this fuel channel 14 32 relative end extends towards the hot-zone, fuel carries out the cold-zone 30 that U-shaped turned to and moved back to the first end 11a in this relative end, and the fuel that consumed is discharged by fuel outlet 16.Similarly, the air that provides from air supply part 36 enters the fuel cell rod by air intake 18 TMDevice 10 the second end 11b also passes air duct 20 and moves, and this air duct 20 32 relative end extends towards the hot-zone, and air carries out U-shaped in this relative end and turns to and move back to the second end 11b, and air leaves cold-zone 30 by air outlet slit 22.Turn to passage by these U-shapeds, the part from initially entering hot-zone 32 to knee (U-shaped turns to) of fuel channel 14 and air duct 20 is formed for heating fuel and preheating of air district.After this knee of process or U-shaped turn to, in passage 14,20, this passage is lined with corresponding anode 24 or negative electrode 26, and anode 24 and negative electrode 26 are with respect to being in electrolyte between them with the relativeness setting, and electrolyte region forms active region 33b in hot-zone 32.Therefore, fuel and air were heated before entering the active region, to improve the fuel cell rod TMDevice 10 efficient, and reduce the use of electrode material to greatest extent.Anode 24 in the cold-zone 30 extends to the outside of described device 10 to connect negative voltage node 38.Similarly, negative electrode 26 extends to the outside of described device 10 to be electrically connected positive voltage node 40.Fuel outlet 16 and air outlet slit 22 also can be in outside the cold-zone 30.
In the numerous embodiments of above-mentioned demonstration and explanation, anode 24 and negative electrode 26 are at the fuel cell rod TMMove in the layer of device 10, mainly move in the central region of each layer, promptly the inside of described device arrives the end of described device up to it.In this end, anode 24 and negative electrode 26 are projected into the fuel cell rod TMThe outside of device 10, anode 25 that exposes and the negative electrode 27 that exposes are connected in contact mat 44 in this place's metallization (for example by the coating silver paste), then electric wire are welded in this contact mat 44.For example, referring to Fig. 4 A to Fig. 4 B.But, may need the fuel cell rod TMLayer in the device 10 is constructed with higher voltage combination (higher voltage combination), shown in Fig. 8 A to Fig. 9 B.Make the fuel cell rod that produces 1KW power if desired TM Device 10, this power equals the product of voltage and current.One of standard is to use 12 volts of voltages, thereby needs 83 amperes electric current to produce 1KW electric power.In Fig. 8 B and Fig. 9 B, use path (via) to interconnect electrode layer to form parallel connection or series combination.
In Figure 34 A to Figure 37, illustrated and made the interconnective selectable execution mode of electrode layer.These selectable execution modes have used along the fuel cell rod TMThe external belt (narrow contact mat) of the sidepiece of device 10, for example silver paste particularly uses a plurality of little bands, and not at the fuel cell rod TMThe inside of device 10 interconnects described electrode layer.By this band technology (striping technique), having formed to provide series connection and/or combination in parallel to obtain the simple structure of required arbitrarily current/voltage ratio.In addition, compare with internal path, described external belt has looser mechanical admissible error, thereby processing is simple.In addition, described external belt may have the resistance lower than internal path (or identical series resistance).Low resistance in the conductive path can make along the power consumption of this path lower, thus described external belt provide make electric power than low-loss ground from the fuel cell rod TMThe performance that device 10 shifts.
Specifically with reference to Figure 34 A and Figure 34 B, illustrated now with the interconnective external anode/negative electrode of series system.Figure 34 A provides anode 24a, 24b, 24c and negative electrode 26a, the 26b that is arranged alternately, the schematically oblique front view of 26c.Along the fuel cell rod TMThe length of device 10, anode 24a, 24b, 24c and negative electrode 26a, 26b, 26c comprise the tab at the edge that stretches out described device 10, so that anode 25 that exposes and the negative electrode 27 that exposes to be provided.Then outside contact mat (or band) 44 is arranged on the fuel cell rod TMThe outside of device 10 also covers on the anode 25 and negative electrode 27 that exposes, best schematic side elevation with reference to Figure 34 B.By anode 24a, 24b, 24c and negative electrode 26a, 26b, the 26c series connection that three pairs are oppositely arranged, fuel cell rod TMDevice 10 provides 3 volts of voltages and 1 Ampere currents.Among Figure 35, have two these structures, and these two structures connect by the long band that the sidepiece along described device 10 extends, and design interconnective external anode/negative electrode thereby provide with series and parallel, and this connection in series-parallel design can provide 3 volts of voltages and 2 Ampere currents.
Figure 36 A and Figure 36 B provide a kind of and have been used for the low series resistance path that is equal to so that the execution mode of low power consumption to be provided.In this embodiment, hot-zone 32 is positioned at the fuel cell rod TMThe middle part of device 10, the first end 11a and the second end 11b are positioned at cold-zone 30.Fuel is by 12 inputs of the fuel inlet on the first end 11a, and air is by 18 inputs of the air intake on the second end 11b.(hot-zone 32 is fuel cell rods in hot-zone 32 TMThe active region of device 10), anode 24 and negative electrode 26 are exposed to the sidepiece of described device 10, and wherein anode 24 is exposed to a side, and negative electrode 26 is exposed to opposite side.Contact mat (or band) 44 is set to cover on the anode 25 and negative electrode 27 that exposes.Then, along the fuel cell rod TMThe length of the sidepiece of device 10 makes the fuel cell rod TMThe edge metalization (metallized) of device 10 arrives cold-zone 30 up to this metalized portion, at this place negative voltage node 38 and positive voltage node 40 is connected to soldered connecting portion 46.Can not optimize anode 24 and negative electrode 26 just to obtaining low resistance, because they also have other functions, for example electrode is necessary for porous, pass and arrive electrolyte 28 to allow air or fuel, and porousness can increase resistance.In addition, electrode must approach, to allow at the multi-layer fuel cell rod TMObtain good layer density in the device 10, and electrode is thin more, resistance is high more.By to the fuel cell rod TMThe edge (sidepiece) of device 10 increases thicker contact mat 44, can provide low-resistance channel towards being welded to connect portion 46.Contact mat 44 is thick more, and resistance is low more.If electronics must be at the fuel cell rod TMFor example move 10 inches along electrode in the device 10, pass all holes (void) of electrode layer, the most low-resistance passage for example for moving 0.5 inch edge that promptly arrives described device 10, moves 10 inches along outer non-porous contact mat 44 then.Therefore, by low resistance conduction path is provided, along the fuel cell rod TMInstalling 10 outsides, long, as to extend to cold-zone 30 contact mat 44 allows low-losses ground from the fuel cell rod TMInstall 10 transfer electrical power.Therefore, can be at the fuel cell rod TMDevice uses described band technology in 10 the active region (hot-zone 32), be used to form string be connected in parallel, increasing power, and allow electric power from the fuel cell rod along the long band that the sidepiece of described device 10 extends to cold-zone 30 TMDevice 10 shifts efficiently.
Figure 37 has shown the perspective schematic view to execution mode similar shown in Figure 36 B, but at the fuel cell rod TMThe first end 11a of device 10 has a cold-zone 30, and hot-zone 32 is positioned at the second end 11b of described device 10.Be provided with a plurality of belts or contact mat 44 in the hot-zone 32, to form series connection and/or to be connected in parallel, 32 to the cold-zone 30 from the hot-zone, be provided with the long band of level or the contact mat 44 that extend along the sidepiece of described device 10, to be formed for being connected to the soldered connecting portion 46 of positive voltage node 40 and negative voltage node 38.
A kind of method that is used to form fuel channel 14 and air duct 20 is that organic material is placed in the green compact layer structure as sacrifice layer, and this sacrifice layer can be discharged by roasting in follow-up sintering step subsequently.In order to make fuel cell rod with high power output TMDevice 10, the power output of 1KW or 10KW for example, fuel cell rod TMDevice 10 must length and width and is had a lot of numbers of plies.For example, described fuel cell rod TMThe length of device can be 12 inches to 18 inches.When the described green structure of roasting was sacrificed organic material with sintered ceramic and removal, the organic material that is used to form fuel channel 14 must be discharged by the opening 12 and 16 that forms fuel inlet and fuel outlet respectively.Similarly, being used to form the organic material of air duct 20 must roasting and discharge by the opening 18 and 22 that forms air intake and air outlet slit respectively.Described device is long more and wide more, with regard to difficult more described organic material is discharged by these openings.If heating is too fast in roasting process, because the decomposition of described organic material is discharged described structure faster than described material, layering (delaminate) can take place in each layer.
Figure 38 A and Figure 38 B have shown a kind of schematic cross-sectional vertical view of selectable execution mode, and this execution mode provides a plurality of outlet gaps that are used for described organic material (sacrifice layer) 72 roastings discharge.Shown in Figure 38 A, at the fuel cell rod TMOne side of device 10 is provided with a plurality of openings 70, to be provided for making organic material 72 discharge a plurality of roasting passages of described structure.Shown in Figure 38 B, after roasting is discharged, by to the fuel cell rod TMThis side of device 10 applies barrier coat 60 and seals a plurality of openings 70.For example, barrier coat 60 can be the glass that contains ceramic packing.In another example, barrier coat 60 can be the contact mat 44 that for example is filled with cream (paste), and this contact mat 44 subsequently can also be as the low-resistance channel that produces electric power.Silver paste can also comprise glass, to improve adhesion.In typical embodiment, the roasting passage that is used for negative electrode 26 leads to the fuel cell rod TMOne side of device 10, the roasting passage that is used for anode 24 leads to the fuel cell rod TMThe opposite side of device 10 is to avoid short circuit between the electrode of opposite.
At the fuel cell rod TMIn the selectable execution mode of device 10,100,200,300, open air duct 20 and fuel channel 14 are not lined with negative electrode 26 or anode 24, but by using the porous electrode material that allows air or fuel to flow through, described negative electrode can with the air duct combination, and described anode can with the fuel channel combination.Described negative electrode and anode must be porous, carry out to allow reaction, thereby in conjunction with the input of forced air and fuel, can pass through described fuel cell rod TMDevice obtains enough fluids, to allow to take place to produce the reaction of electric power.
Another embodiment of the invention is presented in the schematic cross sectional end view among Figure 39.This execution mode mainly is the anode support type fuel cell rod TMDevice 10.Identical with other execution modes, the fuel cell rod TMDevice 10 can have hot junction 32 and cold junction 30, perhaps two cold junctions 30 and middle hot-zone 32.Do not adopt pottery 29 to support described device 10, this anode support type uses anode material as supporting construction.In this anode construction, fuel channel 14 and air duct 20 are with the relativeness setting.Air duct 20 is lined with dielectric substrate 28, and and then is lined with cathode layer 26.Can use chemical vapour deposition (CVD) with the deposition internal layer, perhaps by using sticky plaster solution (solutions ofviscous paste).
Among Figure 40 A and Figure 40 B, shown to be used for the anode support type fuel cell rod TMThe another kind of execution mode of device 10.In this embodiment, removed the fuel channel 14 of independent opening, thereby the anode of porous 24 is also as fuel channel 14.In addition, fuel cell rod TMDevice 10 is coated with barrier coat 60, and for example glass coating or ceramic coating are discharged from the sidepiece of described device to prevent fuel.As required, fuel cell rod TMDevice 10 can have with this anode construction in electrolyte 28 and a plurality of air ducts 14 of being associated of negative electrode 26.Shown in Figure 40 B, fuel passes through anode 24 (anode 24 of porous is as the fuel channel 14) coercively fed of porous to the first end 11a from fuel supply part 34, and through electrolyte 28 and negative electrode 26 with the air reaction of supplying with part 36 from air, and can leave air outlet slit 22 subsequently with the air and the fuel of mistake.
The schematic cross-section end-view of another kind of execution mode is shown among Figure 41 A, and its schematic plan is shown among Figure 41 B, the fuel cell rod TMDevice 10 can comprise a plurality of air ducts 20 that are arranged in the described anode support structure, and fuel channel 14, this fuel channel 14 is vertical with a plurality of air duct 20, to be used for from fuel supply part 34 by 12 pairs of a plurality of air duct 20 fuelings of a fuel inlet.Similarly, air duct 20 at first is lined with dielectric substrate 28, is lined with negative electrode 26 then.Fuel passes anode construction 24 from a described fuel channel 14, pass electrolyte 28 and pass negative electrode 26, with air duct 20 in air reaction, and with the fuel of crossing and air from air outlet slit 22 discharges.Can also ooze out the fuel cell rod that does not comprise barrier coat 60 with the fuel of crossing TMThe sidepiece of device 10, this uncoated sidepiece can be orientated as with respect to a described fuel channel 14 and be positioned at the fuel cell rod TMThe opposite side of device 10.
In relating to the execution mode of anode support structure, be understandable that this structure can be diverted to structure for supporting of cathode basically.Fuel channel 14 is coated with dielectric substrate 28, then anode layer 24 can be set in described cathode construction.Independent air duct 20 or a plurality of air duct 20 can also be set, perhaps the hole of negative electrode 26 can be used for air flows.
Figure 42 A to Figure 42 C has shown the method that forms electrode in air duct 20 and fuel channel 14.With fuel channel 14 and anode 24 is example, not by using green ceramics layer and strap layer to connect the mode of one deck or form green structure by type metal (print metallization) with one deck, among the present invention, at first form the fuel cell rod that does not have electrode TMDevice 10.In other words, use the green ceramics material to form the fuel cell rod TMThe electrolyte 28 and the ceramic support portion 29 of device 10, and use organic material to form described passage, for example fuel channel 14.At the sintering fuel Battery Baton TMAfter the device 10, fuel channel 14 is filled anode cream (anode paste) or solution.Described cream can be thick as printing-ink, perhaps the image height content aqueous solution equally rare (runny).Described anode material can be filled into by suitable mode in the fuel channel 14, for example sucks, is pressed into by capillary force or by air pressure by vacuum.
Selectively, shown in Figure 42 A to Figure 42 C, described anode material is dissolved in the solution, flows into fuel channel 14, then precipitation.For example,, can make the anode solids precipitation, and solution is flowed out by changing pH value.Select as another kind, can allow described anode solids precipitation (settling) simply, then drying liquid or make the liquid roasting discharge fuel channel 14.This precipitation can realize that this printing ink or liquid-carrier can not for example keep suspending with the time that prolongs because of low viscosity makes described particle by forming printing ink or liquid-carrier.Can also use centrifuge to force precipitation.This centrifuge can easily allow most of particles to be deposited in according to qualifications on the surface of fuel channel 14, thereby keeps electrode material and only guarantee that a surface with fuel channel 14 is as electrolyte.
Shown in Figure 42 A, the solution 66 that will comprise the anode particle sucks fuel channel 14, up to filling up this passage 14 fully, shown in Figure 42 B.Described then particle deposition to the bottom of passage 14 to form anode layer 24, shown in Figure 42 C.Compare with normal capillary force, can pass through the inflow that gravity, vacuum or centrifugal force quicken solution 66.Certainly, for example when anode 24 and fuel channel 14, can also use the negative electrode cream of any one selectable execution mode or solution to form cathode layer 26 in the air duct 20.
In another kind is selected, ceramic electrode (male or female) material of lyosol (sol-gel) state can be injected (fuel or air) passage, make this ceramic electrode material be deposited in the inboard of described passage then.For example under the situation that the concentration of the required electrode material in described liquid is lower, can repeatedly repeat described implant operation, perhaps can in electrode, form capability gradient (gradient ofproperty) (with respect to the amount of the YSZ in electrolyte electrode far away and from electrolyte near electrode and the YSZ that different amounts are provided (yttrium stable zirconium oxide), a plurality of layers of perhaps if desired different materials being made put together (for example the close electrolyte of being made by LSM (lanthanum strontium manganite) of negative electrode is used then and covered the top of LSM to obtain better conductivity).
Refer again to Fig. 7 C and Fig. 7 D, wherein, use spheres of ceramic or ball to provide support structure, can also use ceramic particle to increase the active surface zone obtaining better conversion zone, thereby obtain higher output air duct 20 and fuel channel 14.Before the coated electrode layer, can be at fuel channel 14 and air duct 20 inboard very tiny Ceramic Balls or the particles of size that use.As shown in the cross-sectional schematic side view of Figure 43, surface particles 62 is arranged along passage 14, and to provide surface topography uneven dielectric substrate 28, the uneven surfaces pattern has increased the surf zone that can be used for the collecting electrode layer.By applying anode materials around surface particles 62 fully, anode 24 is arranged on the uneven surfaces pattern then, thus the augmenting response zone.
In a kind of selectable execution mode, as shown in the cross-sectional schematic side view of Figure 44, can lamination dielectric substrate 28, thereby provide uneven surfaces pattern or texture table surface layer 64, for example have on the particulate (fine grading) of V-arrangement shape by living dielectric substrate is pressed in, this shape will be attached on the dielectric substrate 28.So that pottery and after texture table surface layer 64 solidifies can apply anode layer 24 (as by using backfill (backfill) operation described in above-mentioned Figure 42 A to Figure 42 C) then, has the anode of conversion zone greatly at sinter electrolytes layer 28 to provide.
Shown also another kind of execution mode of the present invention at Figure 45 A and Figure 45 B.Figure 45 A is the schematic plan that explanation air-flow and fuel flow through air duct and fuel channel and arrangement of electrodes, and Figure 45 B is the viewgraph of cross-section that passes hot-zone 32.Along the fuel cell rod TMThe length of device 10, described device are divided into left side 80 and right side 82, and centre between left side 80 and right side 82 or bridge joint (bridging) portion 84.A plurality of air duct 20L are from the fuel cell rod TMThe first end 11a of device 10 extends through left side 80 along its length and stretches out from the second end 11b that is close to left side 80, and a plurality of air duct 20R extends through right side 82 along its length and stretches out the fuel cell rod at the second end 11b that is adjacent to right side 82 from the first end 11a TMDevice 10.Air duct 20L departs from air duct 20R and is provided with, shown in Figure 45 B.A plurality of fuel channel 14L are from the fuel cell rod TMDevice 10 the second end 11b extends through left side 80 along its length and stretches out from the first end 11a in contiguous left side 80, and a plurality of fuel channel 14R extends through right side 82 along its length and stretches out (exit) from the first end 11a on contiguous right side 82 from the second end 11b.Fuel channel 14L departs from fuel channel 14R and is provided with.In addition, except a fuel channel and air duct, each fuel channel 14L and air duct 20R in pairs and a little skew are provided with, and each air duct 20L and fuel channel 14R are in pairs and skew setting a little.For fuel channel 14L and the air duct 20R that every pair of skew is provided with, metalized portion (metallization) 80 extends to right side 82 along each fuel channel 14L from the left side, and this platingization part is extended along the air duct 20R of skew a little then.Similarly, for fuel channel 14R and the air duct 20L that every pair of skew is provided with, metalized portion (metallization) 80 extends to right side 82 along each air duct 20L from the left side, and this metalized portion is extended along the fuel channel 14R of skew a little then.When described metalized portion when fuel channel 14L or 14R extend, described metalized portion is as anode 24L or 24R, when described metalized portion during along air duct 20L or 20R, described metalized portion is as negative electrode 26L or 26R.The fuel cell rod TMIn the bridge part 84 of device 10, described metalized portion is not extended along any air or fuel channel, and described metalized portion is used simply as the bridgeware (bridge) 90 between anode and the negative electrode.In one embodiment of the invention, described metalized portion can comprise commaterial along its length, and for example anode 24L or 24R, bridgeware 90 and negative electrode 26L or 26R comprise commaterial separately.For example, each metalized portion can comprise platinum separately, and it can be used as male or female well.Selectively, described metalized portion can comprise different materials.For example, negative electrode 26L or 26R can comprise lanthanum strontium manganite (LSM), and anode 24L or 24R comprise nickel, NiO or NiO+YSZ.Bridgeware 90 can comprise palladium, platinum, LSM, nickel, NiO or NiO+YSZ.The present invention relates to be suitable for use as any materials type or the combination of negative electrode or anode, or the connection material between anode and the negative electrode, the present invention is not limited only to the above-mentioned concrete material of listing.
At the fuel cell rod TMOne side (being shown as right side 82) of device 10 at this, fuel channel 14R is provided with the anode 24R that is associated, and this anode 24R extends to the fuel cell rod TMThe anode 25 that the right hand edge of device 10 exposes so that the outside to be provided.Air duct 20L be provided with respect to its skew fuel channel 14R do not have related, so anode 24R need not to extend to the left side 80.Shown in Figure 45 A, outside contact mat 44 covers on the anode 25 that exposes and along the fuel cell rod TMThe length of device 10 extends to cold-zone 30.Can and be welded to connect portion 46 by electric wire 42 then negative voltage node 38 is connected in contact mat 44.Anode 24R can pass hot-zone 32 and extend (as shown in the figure) to right hand edge, perhaps can only extend in small tabs portion to reduce the amount of the electrode material that uses.In addition, anode 24R can extend to the fuel cell rod along the length of fuel channel 14R TMThe right hand edge of device 10, but this execution mode can cause the nonessential use of electrode material.
Similarly, at the fuel cell rod TMThe opposite side of device 10 (being shown as left side 80) at this, an air duct 20L is provided with the negative electrode 26L that is associated, and this negative electrode 26L extends to the fuel cell rod TMThe negative electrode 27 that the left hand edge of device 10 exposes so that the outside to be provided.This air duct 20L is unconnected with the fuel channel 14R that is provided with respect to its skew, and negative electrode 26L need not to extend to right side 82.Contact mat 44 can be along the fuel cell rod TMThe outside in the left side 80 of device 10 extends to cold junction 30 from the negative electrode 27 that exposes, and can and be welded to connect portion 46 by electric wire 42 at this cold junction 30 positive voltage node 40 is connected in contact mat 44.
In Figure 45 B, fuel channel 14R and the anode 24R that is associated are shown as the top that is positioned at right side 82, and an air duct 20L and the negative electrode 26L that is associated are shown as and are positioned at the fuel cell rod TMThe bottom in the left side 80 of device 10.But the present invention is not limited only to this layout.For example, air duct 20L and the negative electrode 26L that is associated also can be arranged on the top of described device 10 and be positioned at left side 80, with it similarly, fuel channel 14R and its anode 24R that is associated skew are provided with, but metalized portion 80 is not passed connecting portion 84 and extended to right side 82 from the left side.But lack bridgeware 90, make anode 24R separate with negative electrode 26L basically.Design extra layout, wherein, the fuel cell rod TMDevice 10 can be provided with and be positioned at independent fuel cell rod TMTwo independent air duct groups (stack) and two independent fuel passage group in the device 10, and battery is connected in series.Execution mode shown in Figure 45 A and Figure 45 B helps increasing voltage under the situation that does not increase electric current, keeps low resistance simultaneously.In addition, this execution mode is at the fuel cell rod TMProvide high density in the device 10.
The perspective schematic view and the schematic sectional view that have shown a kind of selectable execution mode among Figure 46 A and Figure 46 B respectively.Aforesaid execution mode (for example Figure 37) is along the fuel cell rod TMDevice 10 the outside or outward flange 32 30 are provided with external belt to the cold-zone from the hot-zone, so that low-resistance channel to be provided, make electronics move to cold junction.In the execution mode shown in Figure 46 A and Figure 46 B, the band that extends along the sidepiece or the edge of described device 10 is not set, but be provided with contact mat 44 along one in a side and top surface and the basal surface, to be used for the outside anode 24 that connects, another contact mat 44 is along another setting in opposite side and top surface and the basal surface, to be used for the outside negative electrode 26 that connects.Therefore, electronics has obtained bigger or wideer movable passageway, thereby lower resistance is provided.These big contact mats 44 that are arranged on two adjacently situated surfaces can be used for arbitrary execution mode disclosed herein.
Shown the fuel cell rod that utilizes heat exchange principle among Figure 47 TMThe schematic section side view of another execution mode of device 10.Afterwards, fuel channel 14 and air duct 20 are connected to independent discharge-channel 21 at the air of heating and the fuel active region 33b that passes hot-zone 23 (be the anode 24 of hot-zone 32 and negative electrode 26 relatively and the part of electrolyte 28 is set between anode 24 and the negative electrode 26).Any unreacted fuel burns in the time of all can combining at the air with heating, thereby produces extra heat.Discharge-channel 21 is adjacent to active region 33b and 30 extends towards the cold-zone backward, and the inflow fuel that the flow direction of emission (fuel of use and air) and adjacent fuel channel 14 and air duct 20 are interior is opposite with the flow direction of air.The extra heat transferred that produces in discharge-channel 21 is to adjacent passage 14 and 20, with the fuel and the air of heating inflow.
Figure 48 A to Figure 48 C has shown a kind of " end coiling fuel cell rod TMDevice " 400, this device has thick 402, and this thickness of thick 402 is much larger than thin portion 404, shown in Figure 48 A.Fuel inlet 12 and the air intake 18 contiguous first end 11a are provided with, this first end 11a is positioned at thick 402 end, though do not show that air outlet slit 16 and fuel outlet 22 can be arranged on the sidepiece that is adjacent to second opposed end 11b of described device 400, this sidepiece is the end of thin portion 404.Thick 402 should be enough thick, so that mechanical strength to be provided.This can realize by be provided with thick ceramic 29 around adjacent fuel inlet 12 and air intake 18.Thin portion 404 comprises active region 33b (not shown), and this active region 33b comprises the anode (not shown) that is oppositely arranged with the negative electrode (not shown), and has electrolyte (not shown) (identical with the execution mode of front) between described anode and the negative electrode.Thin portion 404 should enough approach, to allow coiling under green compact (unfired) state, shown in Figure 48 B.To approach after portion 404 is wound to required tightness the described device 400 of roasting.The thin portion 404 that can heat coiling then to be inducing reaction, but thick 402 be cold junction, identical with explanation in other embodiments.This end coiling fuel cell rod TMDevice 400 is for being installed in high surface area device in the little space by the thin portion 404 that reels.In addition, the thin cross section of the active region 33b in the thin portion 404 has reduced heat and has outwards transmitted and allowed good temperature cycles along described pottery.
Be exposed to fuel at anode 24 and negative electrode 26 and be positioned at active region (being reaction zone) 32 and or the Battery Baton of 33b TMIn the execution mode at device 10 edge (sidepiece), be positioned at the pottery 29 at the top of described device 10 can be in the active region 32 and/or 33b recessed.This allows negative electrode 26 all can be able to contact from the top with anode 24, is electrically connected to form.Then can be from the active region 32 and/or 33b to the cold-zone 30 along the fuel cell rod TMThe top surface of device 10 is provided with contact mat 44 (for example metal tape), provides connection so that the outside to hot-zone chamber/stove to be provided.
In another embodiment, fuel cell rod TMDevice 10 comprises two cold-zones 30 that are positioned at opposite end 11a, 11b and is positioned at the hot-zone 32 at middle part, be used for the contact mat 44 (for example metal level band) of anode 24 and/or negative electrode 26 can be from the hot-zone 32 outwards towards the fuel cell rod TMInstall 10 fuel cell rods TMTwo end 11a, 11b of device 10 extend, for example shown in Figure 36 B.Can form two independent electrical connections to each anode 24 and negative electrode 26 then.As an example rather than restriction, can use one group of voltage output that is electrically connected and fetches monitoring battery, another group connects and can connect load and allow electric current to flow simultaneously.Battery self has the performance of independent detection voltage, has the advantage of the better theory that a kind of total electricity output that is used for battery is provided.
For contact mat 44 (for example metal tape), can use the electric conducting material that well known to a person skilled in the art that any one is suitable.Object lesson comprises silver, LSM and NiO, also can use bond material.In one embodiment, can be in hot-zone 32 along the fuel cell rod TMThe non-precious metal material is used on the surface of device 10.LSM for example can be used for the place of the air generation oxidation reaction in the chamber/stove of hot-zone.NiO for example can be used for the place of the air generation reduction reaction in the chamber/stove of hot-zone.But in either case, if the non-precious metal material extends to hot-zone chamber/stove outside, the conductivity of this non-precious metal material can weaken, and makes that described metal layer material must be at the fuel cell rod TMDevice 10 carries out the transition to precious metal or corrosion-resistant material before leaving hot-zone chamber/stove.Silver paste is more suitable precious metal material.Further specify, some materials for example LSM can when reaction temperature is reduced to room temperature, become in temperature non-conductive, and other materials for example nickel can when the air of the cold junction 30 that is exposed to described device 10, become non-conductive.Therefore, be used for the fuel cell rod TMDescribed metal level (metallization) material of the contact mat 44 in the cold junction zone 30 of device 10 must (promptly not protected air) and can be conducted electricity at low temperatures in air.Precious metal for example silver passes temperature/air transition district work, makes that described metal layer material can be at the fuel cell rod TMDevice 10 carries out the transition to precious metal before leaving hot-zone chamber/stove.The materials used combination can allow to select material according to the special conductivity needs of hot-zone 32 and cold-zone on the other side 32, and allows to reduce cost by reducing employed precious metal amount.
Shown in Figure 49 A to Figure 49 C, in forming the process of green compact, lead 92 or other physical structures (Figure 49 A) are set in described device, then each described layer of lamination and make and behind lamination, remove lead 92 (Figure 49 C) then in lead 92 location (Figure 49 B).This is useful, for example, at fuel or air intake place, enters the fuel cell rod in air flow passage 14,20 TMDevice 10 hot-zone 32 (reaction zone) before, the fuel cell rod TMDevice 10 can have several inches length.Replace by coating (printing) polymer and make its in roasting technique slowly roasting go out to form described passage, can use described lead technology from the fuel cell rod TMThis part of device 10 solves the problem that occurs in the roasting.As an example rather than restriction, can use diameter is 0.010 inch lead, and this lead is extracted easily.Lead 92 also can be offseted, and to form banded physical structure, this band shape physical structure has the volume similar in appearance to lead, but cross section is littler.Because band has bigger surface area, can on the surface of this band, apply release agent (release agent), adhere to ceramic layer when the lamination to prevent described band.Therefore, term " lead " is used for extension ground and comprises various long and narrow physical structure, and cross section can be circle, ellipse, square, rectangle etc.
Figure 50 A to Figure 50 C has shown a kind of formation one deck fuel cell rod TMThe execution mode of the access road of device 10.In this embodiment, do not use the gap to form and form whole fuel channel 14 and oxidant channel 20 with 94 (for example polymer or wax bands), the gap forms is with 94 only to be used for active region 33b, and promptly anode 24 and negative electrode 26 are oppositely arranged and are provided with the zone of electrolyte 28 between it.Do not have in the inactive area of accordingly relative anode 24 and negative electrode 26 at fuel channel 14 and oxidant channel 20, use lead 92 to replace gaps to form and is with 94.As shown in the figure, lead 92 contact or overlap joint gap form is with 94, makes to be formed with 94 passages that form 14,20 by lead 92 and gap 12,18 to extend to continuously and export 16,22 (not shown)s from entering the mouth.
When the fuel cell rod TMDevice is 10 complicated more, uses that this lead is former to be comprehended usefully more, and for example, it can simplify the multi-layer fuel cell rod TMInstall the roasting problem of 10 complexity.Partly cause is to remove binding agent, the binding agent in labyrinth particularly, and problem is that the binding agent roasted product must produce (decomposition of polymer) position from it and move to the fuel cell rod TMThe outside of device 10.But after extracting lead 92 out described structure, the passage that extends along the gap is empty and clean.If lead 92 (perhaps other suitable physical structures) can be put into labyrinth and therefrom extract out subsequently, then thereby the gap that produces can allow the roasted product in a lot of zones in the described structure to find the passage that leaves described structure rapidly.
The useful purpose of another of described lead principle is to help the dispersion fuel Battery Baton TMPressure in the device 10.When independent pipe to the fuel cell rod TMWhen installing 10 air supplies or fuel, along the fuel cell rod TMThere is different flowing velocities in a plurality of passages in the device 10.For example, if the fuel cell rod TMHave 50 air ducts 20 (corresponding to 50 active layers) in the device 10, then have a passage and have bigger slightly cross-sectional area, and have a passage to have smaller slightly cross-sectional area.This may be to be caused by the change at random that the gap forms the size of material.A solution is the cross-sectional area of every layer of outlet of restriction.If the cross-sectional area of every layer of outlet can accurately be made, make that these outlet cross-sectional areas are identical, and if the cross-sectional area of these outlets all less than the cross-sectional area of input pipe, every layer flow then with identical.This conforms to the practical situation of air stream with fuel stream.Described lead principle can realize this solution.Every layer outlet, insert lead 92 to form the final air duct that is communicated with external environment condition.For 50 layers, insert 50 short leads.When extracting these leads out, every layer has accurate outlet size (for example, diameter is the passage of 5mil (being mil)).
Therefore, the fuel cell rod of the present invention's design TMIn the device 10, the cross-sectional area of every layer outlet is less than the cross-sectional area of flow channel self.The present invention has also designed a kind of multi-layer fuel cell rod TMDevice 10, wherein, every layer outlet is accurately processed, and makes these outlets have accurately identical cross-sectional area on given position.The present invention has also designed a kind of multi-layer fuel cell rod TMDevice 10, wherein all outlet ports area sum is less than the cross-sectional area of inlet.In these execution modes, the cross-sectional area of outlet is restricted to some position that is positioned at described flow channel, but these positions are positioned at after the end of active part of described layer, but is positioned at the fuel cell rod TMBefore the output of device 10.In other words, these outlets of described flow channel must accurately not be positioned at the fuel cell rod TMDevice 10 outlet only need be positioned at some position in downstream, active region.
Hot-zone 32 and hot-zone chamber have been described in aforesaid execution mode.The hot-zone chamber can also be expressed as stove.Cold-zone or cold junction district 30 are positioned at the outside of described stove.Transition region 31 is fuel cell rods TMThe zone of device 10, the zone of this region adjacent in described stove.Shown in Figure 51, the gross thickness of furnace wall 96 is T.The fuel cell rod TMDevice 10 passes this furnace wall 96.The fuel cell rod TMThe length of device 10 in this furnace wall 96 is the X size and equals thickness T.The fuel cell rod TMThe width that passes wall 96 of device 10 is the Y size.The fuel cell rod TMThe thickness of device 10 is the Z size.The purpose of present embodiment is that Z is less than or equal to Y.
According to one embodiment of the present invention, under situation about optimizing, because the fuel cell rod TMDevice 10 pass furnace wall 96, so furnace wall thickness T should be greater than the fuel cell rod TMThe width Y of device 10.If T is less than Y, then when the fuel cell rod TMWhen device 10 passes wall 96, act on the fuel cell rod TMStress on the device 10 may be too high, the fuel cell rod TMDevice 10 may ftracture.
In another embodiment, shown in Figure 52 A to Figure 52 C, size L is transverse to the fuel cell rod TMDescribed device 10 in the plane (being the Y-Z plane) of the length direction of device 10 (100,200,300 or 400) passes the full-size of the part of furnace wall 96.For rectangle fuel cell rod TMDevice 10 (100,400), full-size L can be a diagonal, shown in Figure 52 B.For the tubular fuel cell rod TMDevice 200,300, full-size L can be a diameter.Under situation about optimizing, described size should make T 〉=1/2L.
Thickness T can be made by commaterial (insulation) 98.Selectively, shown in Figure 53, wall thickness T also can be formed by the insulating barrier of a plurality of divisions, and for example three insulating barrier 98a, 98b, 98c make conductivity of heat be optimized in every layer, to obtain best as far as possible temperature transition result.Under the situation with multilayer furnace wall 96 ', the gross thickness T that all layers are put together should be greater than Y and/or more than or equal to 1/2L, but the thickness in monolayer of wall 96 ' can be less than Y and/or less than 1/2L.
In another embodiment, shown in Figure 54, be provided with multilayer furnace wall 96 ", wherein, a plurality of insulating barrier 98a, 98c can separate by air gap 120.In this design, can make high-temperature insulating layer 98c near hot-zone 32, and make lower temperature insulating barrier 98a near cold-zone 30.Between two insulating barrier 98a and 98c, intermediate temperature area is set then, for example corresponding to transition region 31 or preheating zone 33a.This execution mode makes and flows into the fuel cell rod TMDevice 10 air obtains longer preheating zone, needn't enlarge the thermal region of described stove simultaneously.In this embodiment, wall 96 " thickness in monolayer can be less than the fuel cell rod TMDevice 10 passes wall 96 " time the Y size and/or less than 1/2L.But, wall 96 " overall size T (comprising a layer 98a, 98c and air gap 120) should be greater than the fuel cell rod TMDevice 10 Y size and/or more than or equal to 1/2L.Present embodiment has also designed the insulating barrier more than two.
Above-mentioned explanation be under the situation that does not have anode and negative electrode, at first to form the fuel cell rod TMDevice 10, and the method for these parts of backfill subsequently.The reason of doing like this is, some male or female material can be under the sintering temperature of Zr (zirconium) too closely knit (densify), and if density is excessive, then can not obtain good reaction.Perhaps, more at large, if the different parts of described system can not use same temperature variation curve to be able to best sintering, then backfill is essential.
But more difficult is to provide current collector at the top of male or female.Well known to a person skilled in the art that current-collector 122 (shown in Figure 55 A to Figure 55 E described below) is the high-density electrode as the surface portion of male or female.It is the conductive layer or the matrix (being similar to thin electric wire) of high electricity normally, can concentrate electronics and electronics is moved to the desired position.Current-collector 122 can by NiO or LSM or other lower cost materials or even valuable electrode make.But after the backfilling process that is used to form anode and negative electrode, be difficult to be provided with in a usual manner accurate current-collector.But the problem of current-collector is different with male or female.Need make anode and negative electrode porous, this causes risk of overheating; And current-collector needs densification (in order to obtain good electrical conductivity), thereby in essence can be with the Zr sintering.Though can before the backfill current-collector 122 be arranged on the electrolyte 28, make described current-collector be positioned at anode and negative electrode below and contact electrolyte 28, but this layout has hindered the active region that is positioned on the electrolyte 28, causes the waste of active region inevitably.
According to one embodiment of the present invention, shown in Figure 55 A to Figure 55 E, sintering current-collector 122 together is set also, make current-collector 122 be suspended in the fuel cell rod TMIn the space in the device 10.This can be by printing (print) at first top of sacrificing organic layer 72a (for example polymer) with current-collector 122, and the top coating second of covering set electrical equipment 122 is sacrificed organic layer 72b (for example polymer) then, as schematically showing of Figure 55 A.Therefore, current-collector 122 is clipped between two sacrifice organic layer 72a and the 72b, shown in Figure 55 B.Formation fuel cell rod TMDevice 10 is included in the ceramic support structure 29 sacrifice layer/current collector structure is set, shown in Figure 55 C, sintering then, sacrifice organic layer 72a, 72b disappearance thereby make, to form gap 123 and current-collector 122 is stayed in the gap 123 with suspending, shown in Figure 55 D.The easy then male or female with porous is backfilling in the gap 123, to form male or female.Can also use support column 54 (as mentioned above), make the current-collector 122 that suspends be supported on the support column 54, shown in Figure 55 E, mechanical support to be provided or to make localization criteriaization.For this reason, can in the first sacrifice layer 72a that polymer is made, form through hole or little gap intermittently, thereby collector materials can be printed onto in the through hole downwards off and on.After removing binding agent, this filler opening forms support column 54.Selectively, can in the sacrificial polymer clearance material, add the zirconium ball.After sacrificial polymer dissolving, current-collector 122 can and these zirconium balls bondings, and these zirconium clubs are bonded in supporting construction 29, shown in Figure 56 A and Figure 56 B, thereby provide support.The anode 24 or the negative electrode 26 of porous can be backfilling in this space then, shown in Figure 57 A and Figure 57 B, wherein, electrode particle 124 remains on the viscous liquid 126 that is used for backfill, then that described device is dry, and described solids precipitation and through sintering, to form anode 24 or negative electrode 26.If useful, can optionally make described male or female be deposited in a side (by gravity or centrifugal action).
By using the current-collector type of printing hacures (printed hatch line), some variations can take place in the gap size of air duct 20 or fuel channel 14, make described passage in current-collector 122 place's constrictions (pinch) or obstruction.Because at random size changes and has caused this variation in the sintering process.Figure 58 A to Figure 58 C is the microphoto that shows the example of the current-collector 122 that almost causes passage 14,20 obstructions.The effect of passage 14,20 be make flow unobstructed.Though it is bigger that tunnel-shaped is become, this can unnecessarily reduce the fuel cell rod TMThe density of device 10 (thicker passage and thicker layer can reduce the power density of multi-layered devices).According to one embodiment of the present invention,, current-collector can be embedded in the anode 24 and negative electrode 26 of porous in order to be reduced in the possibility of current-collector 122 place's blocking channels 14,20.Shown in Figure 59 and Figure 60, Figure 59 has shown that current-collector 122 is positioned on the surface of anode 24 and negative electrode 26, Figure 60 has shown that current-collector 122 is embedded in the surface of anode 24 and negative electrode 26, if current-collector 122 is embedded in the thickness of the anode 24 of porous and negative electrode 26 (or being embedded in the anode/cathode basically), then current-collector 122 possibility of stopping up gas channels can reduce then.Figure 69 has shown actual current-collector person's movements and expression, and this current-collector is recessed in the male or female of porous.
Shown a kind of method of burying current-collector 122 underground among Figure 61 A to Figure 61 C.At first, current-collector 122 is distributed or be printed on the interim substrate 128.Then, cover this current-collector 122, for example contain the viscous liquid 126 of electrode particle 124 and make its drying by printing paste or backfill with electrode material.At last, remove interim substrate 128.Interim substrate 128 can be the plastic sheet that only adheres to electrode material after drying by suitable adhesion, makes it possible to stir the electrode on the dry plastics and plastics are peeled off.Also can form to be with and realize identical or similar result on 94 by current-collector 122 and anode 24/ negative electrode 26 being placed on the gap of inserting in the described lamination (stack), and in roasting and sintering process, the gap forms is with 94 can disappear, and obtains identical final result.
In the time of on the top that anode 24 or negative electrode 26 is printed on current-collector 122, if current-collector 122 has the tendency of dissolving a little or stretching, the material that then can use different solubilities is (under opposite extreme situations, current-collector 122 can contain the resin material that is dissolved in polar solvent, and the electrode ink of porous can have the resin material that is dissolved in non-polar solven).Preferably limit this stretching, extension, too much can reduce air in the anode 24 of porous or the diffusion in the negative electrode 26 because current-collector 122 is sprawled.Therefore, certain sprawling may take place in current-collector 122, but at least a portion of current-collector 122 should be embedded in the described porous material.Therefore, in the current-collector passage of the present invention's design, the anode 24 or the negative electrode 26 of the recessed porous of the part of current-collector 122, thus minimizing current-collector 122 is projected into the situation in fuel channel 14 or the air duct 20.
At the multi-layer fuel cell rod TMAmong the active region 33b of device 10, should make electrolyte 28 thin as far as possible, for example 10 μ m.But ultra-thin electrolyte can increase the possibility that leakage takes place between the air side of described device and fuel-side.Thin electrolyte can provide higher power, but too thin meeting causes cracking or leaks and provide zero output from described layer.According to one embodiment of the present invention, the key of minimum value of determining the permission thickness of the electrolyte 28 among the 33b of active region is anode thickness and the cathode thickness impression to gross thickness, thereby also influential to overall strength.As an example rather than restriction, the thickness of 100 μ m prevents cracking if desired, and the thickness of each anode 24 and negative electrode 26 is 45 μ m, and then the thick electrolyte of 10 μ m gets final product works fine.45μm+45μm+10μm＝100μm。
At the multi-layer fuel cell rod TMIn the inactive area (passive area) (zone that does not promptly have relative anode and negative electrode) of device 10, need different thickness.This inactive area is used for air distribution and fuel.This is shown as air in a plurality of accompanying drawings and fuel distributes passage to overlap mutually.Still need to have certain thickness herein to prevent cracking, but do not have anode 24 and negative electrode 26, the ceramic electrolyte layer 28 of the pottery 29 here in must specific activity district 33b is thicker.So in the above-described embodiment, the pottery 29 in the inactive area is necessary for 100 μ m, and the ceramic electrolyte layer 28 among the 33b of active region can be thinner, for example 10 μ m.
According to one embodiment of the present invention, a kind of method that obtains having the independent dielectric substrate 28,29 of two thickness is provided: nonactive air duct has thicker pottery 29 in the zone, and has thinner ceramic electrolyte 28 among the 33b of active region.Shown in Figure 62 to Figure 62 A, this method uses three pottery band 130b to form pottery 29 in nonactive air flow region, wherein, two strap 130a, 130c stop and only middle part band 130b continue to extend to active region 33b, with as relative anode 24 and the ceramic electrolyte 28 between the negative electrode 26.
The multiple design of the slim-lined construction that stretches out the stove that is used for the low temperature connection above has been described.But a lot of designs also can be used for not stretching out the multi-layer fuel cell rod of described stove TMInstall and/or have the multi-layer fuel cell rod of tabular or analogous shape TMDevice.Can realize the density of attainable device among the present invention in other fuel-cell device that in stove, hot fuel-cell device formation is connected and the system.For example, principle disclosed herein can be used for other fuel-cell device, described principle comprises polymer belt, is filled with the polymer belt of ball, is used to form the lead of exit passageway, a passage that is used for two electrodes, foliaceous device, when using gravity or centrifugal force electrode suspension towards a side drying, be used for the sidepiece gap and the series design of terminal.
Current-collector 122 is used for allowing the electronics in that described electrode (anode 24 and negative electrode 26) produces or consumes to move to load (voltage node 38,40) along low-resistance channel.The conductivity of desirable electrode design is not very good, because must allow some phenomenons to take place simultaneously: have the hole to allow air flows, have pottery in the described electrode allowing oxonium ion, and have electronic conductor (electronic conductor) and flow to allow electronics towards electrolyte flow.Compared with the electrode of only being made by electronic conductor, the existence of hole and pottery means that described electrode has higher resistance on the whole.
In a single day electronics is released, and it is very important allowing electronics to move along the high conductivity passage.The existing design of current-collector is based on from conductor and removes electrolyte ceramics, but still leaves hole.This has produced the better layer of conductivity.This layer is printed on the whole male or female.In sandwich construction, a shortcoming of this design is, if must increase the anode/cathode material behind sintering, then is difficult to produce two significantly layers, as mentioned above.Above illustrated and made the current-collector advantage of sintering together.
According to one embodiment of the present invention, can use and comprise that the high density conductor material (is the few or imporosity of hole, if thereby printing on whole anode 24 or negative electrode 26, then can stop the reaction carry out) current-collector 122, this high density conductor material is printed in the hatching pattern (hatch pattern).In one embodiment, described current-collector is printed in the straight-line pattern (also being hatching pattern), and is being used for leaving open space between the shade mark of air penetration.The anode 24 of porous and the gas permeability in the negative electrode 26 make the air that enters at the porous material between the hacures to flow below hacures.By the distance between change line and the line and the width of line self, the geometry that can be optimized.For example, can use 0.006 " live width and 0.030 " line-spacing.Figure 63 has shown the vertical view of the current-collector 122 with hatching pattern.Figure 64 has shown the end view of the current-collector 122 on porous anode or the negative electrode.Figure 65 shows oblique view (angled view), has shown that order from the top down is: current-collector shade, top porous electrode, electrolyte, bottom electrode (giving prominence to (stick out) from electrolyte owing to rupture).When the active region becomes big, can change the live width in the zones of different.Less conductor lines can incorporate bigger conductor lines, and bigger conductor lines can incorporate bigger conductor lines.
Above illustrated and be used for fuel supply part 34 and air supply part 36 are connected to the fuel cell rod TMThe flexible supply pipe 50 of device 10.By supply pipe 50 is trailed, supply pipe 50 can be at the fuel cell rod TMGo up for one among end 11a, the 11b of device 10 and slide.Can be fixed by binding agent.Selectively, according to one embodiment of the present invention, make the fuel cell rod TMDevice 10 forms end 11a (and/or 11b) and has recess (identation) 132 at sidepiece, shown in Figure 66 A to Figure 66 B, thus the fuel cell rod TMDevice 10 can keep supply pipe 50 to go up in position automatically.This most convenient is by router (router) or end mill processing fuel-cell rod under green state TMDevice 10 is realized.
Based on this, as shown in the top, schematic sectional view and perspective view of Figure 67 A to Figure 68 B, also can use can clamping fuel cell rod TMThe connector 134 of the end 11a (and/or 11b) of device 10.Connector 134 can (fuel cell rod TMDevice 10 design) with electric contact (contact) 136 and air flow passage 138 in one or two, gas-tight seal (for example O shape encloses 140) and one or two electric contact 136 that contacts described contact mat 44 be injected into one.If fuel cell rod TMDevice 10 is for having the fuel cell rod at two ends TMDevice 10, then fuel cell rod TMEvery end of device 10 is a polarity, then at the fuel cell rod TMEvery end of device 10, connector 134 still can have two or more electric contacts 136, so that low resistance contact to be provided.Electric contact 136 can be positioned at the fuel cell rod TMInstall 10 sidepiece or be positioned at the fuel cell rod TMThe top and the bottom of device 10 are because be positioned at the fuel cell rod TMThe described electric contact of the bottom of device 10 is wideer, thereby lower resistance can be provided.
Though do not show among the figure, connector 134 can have two O shape circles, thereby two sealing areas are provided in connector 134: one is used for air, and another is used for fuel.This connector can be used as single-ended (single-ended) fuel cell rod TMThe independent connector of device 10 provides positive pole and negative electricity contact and carries air and fuel.
Above-mentioned execution mode comprises two relative end 11a, 11b that are used for described device.But, the fuel cell rod of above-mentioned explanation TMThe principle of device 10 also can be used to have more than two stretches out the end of described stove or the device 500 of outlet.For example, Figure 68 A to Figure 68 B has illustrated the device with 4 outlets.These four positions can be provided with air intake 18, air outlet slit 22, fuel inlet 12 and fuel outlet 16.This feasible unburned fuel is circulated in the stove heating operation is more prone to.Can use more than two and four exit points for example three or six.
Fulcrum ball (referring to Fig. 7 C to Fig. 7 D) can also be used for the fuel cell rod TMOther fuel cell rod outside the device 10 TMDevice, for example rectangular slab device.Described fulcrum ball allows to produce bigger zone in sandwich construction, and different layers is overlapped mutually.Described device can have big open area in the similar multi-layer sheet.Perhaps, described device can have and occupies passages in described zone, 0.5 inch wide, many inches long.Which kind of situation no matter, playing skill art disclosed herein all is favourable.
The key point of described ball scheme is that ball is circular, and it can prevent to puncture.Because need to make thin electrolyte, anode and negative electrode (consider, and for higher performance), so may occur because of the material that uses non-regular shape puncturing for density.The grains of sand or sand grains enter electrolyte and can cause leaking.On the other hand, electrolyte can gently deform around described ball, and can not cause leaking or tearing.Similarly, the support column principle shown in Fig. 7 A to Fig. 7 B can be used in the multi-layer fuel cell structure, and is not limited only to the fuel cell rod TMThe form of device 10.
In Figure 38 A to Figure 38 B, shown and used a plurality of roasting outlets that these a plurality of roasting outlets can used the back sealing.This all is favourable for any multilayer Study of SOFC or other fuel-cell device.In addition, consider big template, the designer can design very big zone for air duct, and need remove the organic material of filling these spaces.But, as a rule, have only a fuel inlet and a fuel outlet.Also be the same for the entrance and exit of air.Big zone has organic material, but outlet seldom, and this may make making one of greatest problem of being faced is how to avoid layering.
The scheme that addresses this problem is to increase can allow air or liquid (using the situation of wax) roasting are gone out described structure and form a plurality of roasting mouths, the little opening of minimum stress on total.After the sintering of multilayer structures, be easy to be returned to this state (come back) and in these little roasting mouths, fill solid material (for example glass-ceramic compound), in case stopping leak leaks.
The principle of lead 92 is very similar to above-mentioned roasting principle, and sandwich construction is highly profitable.Imagination is made the square plate of 4 inches of the length of sides, has 20 or 50 active layers in the plate.You can want to be formed for the roasting mouth of easier removal organic material.If but these easily the roasting mouth can arrive the middle part of described plate, then can be better.This can be by inserting lead 92 and behind lamination it being pulled out realization.Lead 92 can traverse a plurality of zones, if by line 92 crosscuts, can have very long distance between the middle part of described plate and the external world.This principle must not be above-mentioned lead.Lead is the form of most convenient, because it has less surface area.Actual parts can be flat, for example 0.002 " thick, 0.200 " wide.In this case, may need release agent application, to prevent bonding between layer and the layer.But this method is that the parts with reality insert described structure and subsequently with its removal, thereby is convenient to remove organic material.
In another embodiment, use carbon ribbon (carbon tape) to form and be with 94 as the gap.Problem is to make the gap to form the even discharge of material and can cause the fuel cell rod TMCracking or layering appear in the device 10.If this material can disappear and stay open channel then can be better, thereby other polymeric material in anode 24, negative electrode 26 and the electrolyte 28 can be gone out in roasting in good time.A kind of method is to use wax.The employed wax work of hot investment casting is good, fusing about 90 ℃, and the stratification temperature of described sandwich construction layering when this temperature is higher than, but be lower than 150-300 ℃ of binding agent sintering temperature.But wax is unsatisfactory, because if cast the thick thin slice of 2mil, the insufficient strength of wax with wax.One touch promptly broken.The wax of thin portion is should intensity higher.The scheme that addresses this problem is to sneak into certain fiber to obtain certain intensity in wax.Carbon fiber is a kind of selection.Carbon fiber can acquisition from random fibre structure (i.e. pad) or textile fabric structure (being similar to cloth).Also can use other fiber.Can obtain best performance by wax being immersed carbon fiber.This carbon/wax compound can be inserted described sandwich construction to form the gap.Behind the lamination, temperature rises to the fusing point of wax, and wax becomes liquid state and flows out the fuel cell rod then TMDevice 10.This can stay open air duct in carbon fiber, polymeric material roasting easily around allowing, that be positioned at described structure is gone out.Carbon fiber can not volatilize before temperature reaches 750 ℃ and (become CO 2).Therefore, can form a kind of structure, wherein, main gap forms material and disappeared before roasting goes out binding agent, thereby for removing binding agent leaving gap passage.Then, when medium temperature, polymer self volatilization.Finally, when high temperature, carbon fiber disappears.The picture of leaving gap when Figure 70 is to use this carbon-wax compound to carry out eliminating wax and carbon fiber behind the sintering.
Realize in multi-layered devices that preferably high electric current connects.Realize that in multi-layered devices interconnective a kind of method is to use via hole (via hole).Can fill this via hole then by be with boring on 130 at pottery, to form the path 56 shown in Figure 71, the insulating barrier that perhaps can pass printing forms path, but oven dry back effect is the same.Shown the connection that path 56 forms among Figure 71, this connection links together two electrodes (anode 24 or negative electrode 26).Hereinafter in the explanation,, use execution mode with two electrodes 24 for for simplicity.Path 56 helps transmitting the signal of telecommunication, transfer of data for example, but not ideal for transmitting electric power or high electric current.In order to be used for electric power or high electric current, need a plurality of parallel paths 56 to have the effect that reduces all-in resistance.According to one embodiment of the present invention, the improved method that is used to transmit electric power or high electric current is the whole zone of removing the green compact band that is used to separate conductor.Adopt this method, interconnecting can be based on very big zone.In Figure 72, interconnect to be shown as and be positioned between two electrodes (anode 24), by between two electrodes (anode 24), removing pottery band or material 130 fully.Because described layer (no matter being belt or printed layers) is soft under green state, so described layer can deform.If desired, can extra ceramic material be set, thereby in anabolic process, keep the overall flat of pottery in above-mentioned interconnective zone.
Trickle change is that punching goes out macropore 142 in green ceramics band 130, shown in Figure 73 A, then pottery is with 130 to insert multilayer modules, perhaps selectively, printing have the insulating barrier of macropore 142 and subsequently with conductor printing to the top.In multilevel method, described electrode hangs down in the macropore 142, forms bigger contact area, shown in Figure 73 B (electrode that is arranged in the below also can be displaced to hole 142 up).The difference of this execution mode and above-mentioned via hole is that the zone of via hole is very little and must fill this zone separately.In addition, have via hole, the electrode of top and bottom can not be out of shape and is displaced in the described hole.
Therefore, embodiments of the present invention have been imagined a kind of fuel cell rod TMDevice 10, wherein, by removing insulating material or providing the zone of naked material to form mutual electrical connection, wherein, be arranged in the conductor distortion on every side (for example upside and downside) of insulating material and be displaced to the cavity area (voided area) of naked material, to be in contact with one another.Conductor contacts in this cavity area, and this cavity area can be from the fuel cell rod TMThe inside of device extends to the edge of described device always.Can insulating regions be removed in the specific region, for example portal or cut out special shape, for example rectangle by punching press.
According to another kind of execution mode, on a layer, form being connected in series of battery, this helps increasing the fuel cell rod TMThe voltage output of device, and pass through the work about electric power that produced easilier.For example, if Battery Baton produces 1KW electric power, easier design electronic products and the easier balance that designs factory make it can handle 1000V, 1A, rather than 1V, 1000A.As schematically showing of small scale among Figure 74 A, the part of green ceramics (for example zirconium) with 130 used at the middle part, and top and bottom are anode 24 and negative electrode 26.Pore in independent hatching pattern (with being used for the identical of prior figures anode 24 and negative electrode 26) expression anode 24 and the negative electrode 26, the hatching pattern of overlapping is represented atresia conductor (for example conductivity ceramics, precious metal or non-oxide metal alloy).Described battery exists only between the porous zone 144, shown in independent hatching pattern, because aporate area 146 can not touch fuel or air.
Figure 74 B has shown how a plurality of parts are set together (being called principle is because can not keep tilting, but the explanation on the principle is used to show the overlap joint of this design) from principle behind lamination.In three batteries of this group, in order to illustrate rather than to limit, the top side of each unit (or part) comprises anode 24, and the bottom side of each unit (or part) comprises negative electrode 26.If regard each unit as baby battery, then the string of three unit formation can be regarded three batteries of series connection as.Can have fuel supply part 34 on one side of this series design, have anode 24 on the top, have air on the opposite side and supply with part 36, have negative electrode 26 on the bottom.Can prevent that air from leaking from a side direction opposite side, this can be provided with aporate area 146 and realize by the end in each unit (or part).A plurality of unit (or part) can be set together by this method, to obtain required free voltage.
Figure 74 C has shown the more accurately view of described layer behind lamination.Described layer is flat basically, but has extra thickness in lap-joint.Figure 74 D has shown the principle schematic of three batteries (or part) designs.Each vertical arrow is represented a battery, and the direction of arrow limits polarity.There is not the line of arrow to represent not produce interconnecting of any voltage.The roughly direction of representing electric current along the horizontal arrow of bottom.The present invention is not limited only to three batteries (cell) design.Execution mode shown in Figure 74 A to Figure 74 D is called bridging method at this, and two or more (for example 5 or a plurality of battery, 10 or a plurality of battery, 20 or a plurality of batteries etc.) battery can be used to be connected in series.
Figure 75 A to Figure 75 E has shown the selectable method that forms series design, is called conductor (plunging conductor) method of inserting at this.Replacement is with 130 to cut into a plurality of parts and overlap these parts to form series-connected cell on pottery, this method has been used and has been formed continuous pottery with 130 sheet, the anode 24 that this pottery has a part with a side of 130 sheet, opposite side has relative negative electrode 26.The conductor electrode 148 (for example conductivity ceramics, precious metal or non-oxide metal alloy) of sheet shape (be also referred to as and interconnect part, conductive strips or insert conductor) passes pottery and is with 130 to insert.Conductor belt 148 can be the green compact band spare of for example being made by LSM.Be with in 130 at pottery to form slit 150, shown in Figure 75 A, a bit of insertion of conductive strips is passed pottery with 130 centre position.
Shown among Figure 75 B that continuous pottery is with 130 end view.In this explanation, term " electrolyte sheet " or " electrolyte band " all are interpreted as pottery and are with 130.The top surface of electrolyte sheet 130 is anodes 24 of two parts.The basal surface of this electrolyte sheet is respectively with respect to the negative electrode 26 of two parts of the anode 24 of two parts.For with two part series connection, with reference to Figure 75 A and Figure 75 B, first conductor belt 148 passes slit 150 and inserts electrolyte band 130, thereby can think that first conductor belt 148 passes electrolyte and inserts.Next, shown in Figure 75 C, the conductor belt 148 crooked anode 24 of a part (or battery) and the negative electrodes 26 of another part (or battery) of covering.Then, shown in Figure 75 D, make connection electrode be pressed into anode 24 and negative electrode 26, promptly battery carries out lamination with the series connection form.Figure 75 E has illustrated the top perspective of lamination series-connected cell, has more clearly illustrated the whole zone that overlaps.Advantageously, each battery is made by weak point, wide part, thereby reduces the resistance from a battery to adjacent cell.
According to another kind of execution mode, will interconnecting part (conductor belt) 148, to be divided into a plurality of parts be useful.Replace the independent slit 150 in the green compact electrolyte band 130, can use a plurality of short slits 15, a plurality of parts of conductor belt 148 are passed a plurality of short slits 150 respectively and are inserted, shown in Figure 76.Thereby provide a plurality of insertion conductors.
In Figure 75 A to Figure 75 E and Figure 76, the material that interconnects that inserts electrolytical conduction should be an atresia, with prevent or stop air from an electrolytical side flow to opposite side.On the other hand, anode 24 and negative electrode 26 can be porous, and it both can be the complete porous that does not have aporate area, also can have aporate area 146 with the end that interconnects part 148 overlap joints.Make anode 24 and the negative electrode 26 complete porous can be easier, thereby can make material with processing step still less.Figure 77 has schematically shown by interconnecting part 148 and has connected the end view of four parts (or battery) that described battery is connected in series, according to the execution mode of Figure 75 A to Figure 75 E and Figure 76, insert electrolytical part 148 each battery of connection that interconnect by passing.Therefore, can use the battery that interconnects part 148 series connection any amount, comprise two or more, for example five or a plurality of battery, ten or a plurality of battery, 20 or a plurality of batteries etc.
Figure 78 A to Figure 78 C has shown and has been used for along the change of the insertion conductor technology of the individual layer series connected battery of multi-layer cell above-mentioned.In this embodiment, shown in Figure 78 A, anode 24 and negative electrode 26 parts have the fuel cell of extending to rod separately TMInstall the aporate area 146 away from fuel flow channels and air flow passage of 10 sidepieces.Slit 150 in the electrolyte band 30 forms and is positioned at the fuel cell rod TMOn the sidepiece of device 10, rather than the fuel cell rod TMOn the periphery of device 10.Pass the conductor belt 148 that electrolyte band 130 connects anodes 24 and negative electrode 26 and can only be placed in the side margins (margin) and away from described flow channel, before the lamination shown in Figure 78 B, behind the lamination shown in Figure 78 C.
Aforesaid execution mode (for example Figure 71) describes in detail by forming via hole and fill the purposes of the path 56 that this hole forms by printing electrode in green ceramics band 130.Be used for along the be connected in series execution mode of anode 24 and negative electrode 26 of the individual layer of sandwich construction of the present invention, shown in Figure 79 A, first conductor 152 can be printed on the fuel cell rod from the electrode (for example anode 24) of 56 to batteries of filling vias or part TMOn one side of device, second conductor 154 can be from filling vias 56 to adjacent cell or the comparative electrode (for example negative electrode 26) of part be printed on this fuel cell rod TMOn the opposite side of device.Except being used for the material of electrode, also can in filling vias 56, fill other material.In the illustrated embodiment, path 56 is filled with the atresia conductor.
The another kind selection of inserting electrode is wide path or rectangular path 156, shown in Figure 79 B, can form this path 156 by form rectangular via hole in electrolyte band 130.This rectangular path 156 is that with the difference of common path 56 common via hole is round.This rectangular via hole can form wide as required, for example has identical size with the slit 150 that being used to shown in Figure 75 E or Figure 76 inserted electrode 148.Can fill rectangular path 156 in this way, make its allow air from a side flow of dielectric substrate to opposite side.
Use the potential problems of via hole to be, the contraction of material in the hole may be inhomogeneous or greater than the contraction of carrying material, this can allow air to move by side to opposite side from one.Therefore, in selectable or other execution mode, via hole (no matter be circle or rectangular) comprises that the plunger that is positioned at top and/or bottom is to improve bleeder resistance (leak resistance).The example of path with improvement of plunger is shown among Figure 79 C.When having plunger 158a and 158b, plunger can only produce extra sealing in a side (for example top), and when having plunger 158c and 158d, both sides all produce extra sealing.Plunger 158a, 158b, 158c and 158d can obtain by one or more print steps, perhaps obtain by batch operation.According to typical embodiment, the material that is used for via plug transmits for this material can stop air, as in pore-free material.When in conjunction with porous anode 24 and negative electrode 26, last part is shown in Figure 79 D, and wherein, closely knit shade material is an atresia, and the same among the figure of the material that is limited by shade and front, is porous.
Connect the expansion of the execution mode of individual layer as above-mentioned with series system, use the fuel cell rod TMMultilayer in the device 10 can form and be connected in parallel.Figure 80 has shown one group of individual layer that stack, that be connected in series, and wherein, the layer that stacks is also parallel with one another, and in parallel the electrical connection by several right anodes and the vertical line between the negative electrode 160 shows.Insert conductor 148 though some are connected in series to be shown as, also can use other link.In illustrated embodiment, there are three active layers, each active layer is formed by four batteries (part) series connection.Therefore, have 12 batteries in the diagram.Can supply with two different cell channel by a fuel channel, to increase density.Layer with layer battery polar relative: in top layer and the bottom, negative electrode is up an arrow to the direction of anode; In the intermediate layer, negative electrode is down an arrow to the direction of anode.In present embodiment and other execution mode, thisly will public fuel channel be used for electrode pair, make layer with layer the relative feature of polar orientation provide and obtained more highdensity fuel cell rod TMThe method of device.
Shown being connected in parallel along the cross section of the 80A-80A line intercepting of Figure 80 between two negative electrodes 26 or two anodes 24 among Figure 80 A, Figure 80 B has shown perspective view.Male or female to can be simply by allowing male or female to connecting 160 and connect to form the edge in the EDGE CONTACT of fuel channel or air duct respectively.Vertical line among Figure 80 represents that the edge connects 160.In the execution mode shown in Figure 80 A, the edge connects 160 and is arranged in both sides (left side of Figure 80 A and right side); But, only connect and also can realize being electrically connected in a side.This connection makes two anodes 24 or negative electrode 26 parallel connections be electrically connected.Can also use path to connect or other method of attachment.With reference to the passage of the some B among Figure 80 to some B, put B and connect by conductor, make channel B have identical current potential.In Figure 81, channel B is expressed as straight line.The net effect of the battery arrangement among Figure 80,80A, the 80B is a large amount of series connection and combination in parallel, shown in Figure 81.If a battery in the described device or interconnect part and lost efficacy, this layout is useful for conversion electric power.Electric current and voltage can be around damaging or becoming bad zone flows to another function battery.
Figure 82 has schematically shown the single layer fuel Battery Baton of the cascaded structure with bonding layer TMThe cross section of device 10 is as front more detailed description in Figure 74 C.Pottery 29 forms top cover and bottom, and has shown desirable air duct 20 and desirable fuel channel 14.Among Fig. 1, air outlet slit 22 and fuel outlet 16 are perpendicular to illustrated plane.As schematically showing among Figure 83 A to Figure 83 B, this device can also be by a large amount of strings-and series-parallel connection mode combination, as the front the execution mode as shown in Figure 80 to Figure 81 illustrated.Among Figure 83 A, can make dotted line from air duct and fuel channel edge connecting portion 160, shown in Figure 80 A and Figure 80 B.In addition, provide high density structures, wherein, battery can be that to connect also can be in parallel, therefore alternating polarity between the layer of battery as shown by arrows, and has following advantage, if i.e. certain battery failure, then electric current can be carried by the passage around this battery, shown in Figure 83 B.
Illustrated another kind of among Figure 84 A and Figure 84 B at the execution mode that is connected in parallel of between two electrodes on the same air duct, providing convenience.This respectively two anodes 24 or two negative electrodes 26 on the both sides of fuel channel 14 or air duct 20 make.Used the example of two anodes 24 among Figure 84 B.Anode 24 is connected in the central region of fuel channel 14, and only is connected in the sidepiece of passage 14 unlike Figure 80 A.Can form middle part connecting portion 162 simply by hole or gap 164 are set in being used to form the sacrifice gap band 94 of air duct.This hole can be circle or rectangle (for example slit shown in Figure 84 A), and a plurality of holes can be set.Behind lamination and the sintering, top and bottom anode or negative electrode can touch the zone that has gap 164.Advantageously, middle part connecting portion 162 forms and makes this middle part connecting portion 162 can significantly not reduce activity (active) zone in fuel cell zone.
Multi-layer helical pipe fuel cell rod for main employing series design with reference to Figure 28 A to Figure 28 D explanation TMDevice 200 is at helix tube fuel cell rod TMIt is favourable that the outside of device 200 forms two electrical connections.This permission is connected to the cold-zone from anode spot and negative electrode point the most easily.If helix tube fuel cell rod TMDevice 200 is wound up as and makes an end of this series connection group be positioned at the outside of twining volume, and the other end is positioned at the inboard, then can more difficult inboard the connection.This is because gas connection pipe is arranged on helix tube fuel cell rod TMOn the end of device 200, need be positioned at the inboard but be electrically connected.Therefore, if two electrical connections all are positioned at outside meeting better.The helix tube fuel cell rod that has schematically shown non-winding-structure among Figure 85 A TMDevice 200, be connected in series (also schematically showing by arrow) be by making the series design initial sum end at the outside of wrapping range, and extend internally and form U-shaped and turn to and realize.
The independent rectangle block of independent battery 166 usefulness shows.This block is short and wide, thereby has low resistance (end of each battery and the conductive lengths of end are short, but wideer zone allows bigger electric current).Two kinds of methods that this design and above-mentioned formation are connected in series (overlap, or have the insertion conductor that passes dielectric substrate) can be used in combination.With regard to the arrangement of fuel channel 14 and air duct 20, most convenient be to make these passages enter and connect subsequently and draw together along public passage 167 from sidepiece.Shown among the figure and be used to reel helix tube fuel cell rod TMThe mandrel 168 of device 200.Can after lamination and wax fusing, remove then with sacrificing wax coating mandrel 168.Net shape shown in Figure 85 B, helix tube fuel cell rod TMDevice 200 have from the outside towards central part extend, and and then the channels in series that withdraws from toward the outer side from central division again.Represent single battery 166 with arrow among the figure.
Be used to form helix tube fuel cell rod TMThe another kind of method that is connected in series of device 200 is along pipe fuel cell rod TMThe length of device 200 forms series line.In the not winding-structure shown in Figure 86 A, can schematically show channels in series with arrow.Because the non-constant width in active region, so the back battery 166 of reeling can extend to the outside from the inboard of pipe.In the present embodiment, use a plurality of short conductors 148 of passing the electrolyte insertion to form and be connected in series.Independent insertion conductor 148 allows to make that in moulding, coiling and lamination step dielectric substrate has higher intensity.But, also can be connected in series with the formation of the overlap shown in Figure 74 C.Figure 86 B has schematically shown the final winding form of present embodiment.Shown in Figure 85 B, arrow is represented single battery 166.
In this special coiling design, the layer that uses two series connection is to increase pipe fuel cell rod TMThe bulk density of device 200 is favourable.But, must not have plural shunt layer, because described layer can fold itself.Figure 87 A is the schematic side elevation of a long single battery 166 among Figure 86 B, is shown as this battery and extends from left to right.When two layer structures (two dielectric substrates 28, two negative electrodes 26, two anodes 24, air duct 20, a fuel channel 14) are wound on himself, shown in Figure 87 B, the top ingress of air passage 20 of bottom cathode 26.Therefore, more than two-layer be unnecessary.It will be understood by those skilled in the art that instruction, can make pipe fuel cell rod by above-mentioned execution mode TMDevice 200 combinations that are designed to comprise with a plurality of series design of parallel way work.
Another kind according to the present invention is used for helix tube fuel cell rod TMDevice 200 or concentrate tube fuel cell rod TMDevice 300 provides the execution mode of electrical connection, fuel cell rod TMConducting end 170a, 170b can be made in the whole end of device, shown in the coiling of do not reel schematic structure and Figure 88 B of Figure 88 A, spirality (for example) tubular construction.For this reason, at pipe fuel cell rod TMThe end of device 200,300 replaces insulating ceramic materials with electric conducting material.This electric conducting material shows with the shadow region, and can be for example LSM or the contraction matching materials that mixed by two or more separate material, for example LSM and YSZ mixture, and this is comprising most of pipe fuel cell rod TMCoupling contraction better in the sintering process of the pottery 29 of device 200.Particularly, in first battery and last battery of series design, the middle part of the electrode of coiling must contact with being connected in extraneous connector, as the outermost layer of this battery.The conductive region 170a, the 170b that show with shade allow to form this connection effectively.The selectable method (not shown) of contact internal electrode part is at the fuel cell rod TMBoring and backfill electric conducting material in the device.
The layout of the gas flow channel 14,22 of the execution mode shown in Figure 86 A and Figure 88 A can be shown in Figure 89.In order to supply with the active region, gas can enter Battery Baton and arrive bigger public passage 167 at inlet 12,18, and branch is to be used for each independent battery 166 then.Among Figure 89, gas enters public passage 167 and leaves from a plurality of subbranches, but is opposite among Figure 85 A.
At the fuel cell rod that comprises series connection part (or battery 166) TMIn the device 10, and easily be installed in a fuel cell rod TMCompare in the length of device 10, it is useful having higher voltage (more parts).In this case, according to another embodiment of the invention, these series connection parts are being left Battery Baton can orientate as before providing electric power to external world along the dual reciprocal setting of the length of Battery Baton.Figure 90 is the fuel cell rod TMThe schematic side elevation of device has shown that 15 parts (battery 166) how will connect are arranged in the device, mainly is by passage is folding two positions.Also a plurality of this parts can be arranged on a fuel cell rod TMMake that 15 parts are parallel with one another in the device 10.
According to another kind of execution mode, foldover design provides the multilayer with series connection to form the fuel cell rod TMThe another kind of method of device 10.Figure 91 has shown the dielectric substrate 29 of six batteries 166 with series connection with perspective view.These batteries both can also can connect by illustrated insertion conductor method by bridging method.For this chip architecture is installed in the fuel cell rod TMIn the device 10, can be by the folding dielectric substrate 29 of for example folding mode.Observe the end of chip architecture, Figure 92 A has illustrated the knee between the battery 166, and this knee shows with arrow.Along the arrow bending, battery pack begins to form the folded stack shown in Figure 92 B left side.Further compress folded stack, then form the folded stack that compresses 172 shown in Figure 92 B right side.The folded stack 172 that compresses can be placed on the fuel cell rod easily then TMIn device or the multi-layer fuel cell.Series connected battery quantity is only limited by designer's wish.By arrange group horizontal or vertically, multilayer folding heap 172 can (promptly electricity is in parallel) in parallel be placed on the fuel cell rod TMIn the device 10.The gap forms material (for example the gap forms and is with 94) and can be arranged on anode 24 and the negative electrode 26, removes from gas passage 22 and fuel channel 14 as expendable material then.
For matched coefficients of thermal expansion (CTE), it is useful making the one or both sides of folded stack 172 device materials (just top cover or lateral edges) around being not attached to, thus have freely suspend regional.In the execution mode of folded stack design, first battery in the folded stack 172 and last battery are connected in the top cover and the bottom of described Battery Baton, but do not connect all or part of of middle part of described folded stack.Shown the fuel cell rod among Figure 93 A and Figure 93 B TMThe cross section of device 10.In the design that Figure 93 A shows, the left side of folded stack 172 does not connect the left wall of described device, but in the bent intermediate zone, the right side of folded stack 172 is anchored the right wall in described device.This can allow described layer away from described wall, thereby when the described device of sintering, allows folding layer to shrink with the speed different with the material (cover material) of lid.Shown similar structure among Figure 93 B, difference is two end cells except folded stack 172, and folded stack 172 is not connected with right wall with the Zuo Bi of Battery Baton.In these two kinds of execution modes, advantage is and can disposable gas (air or fuel) be offered a plurality of electrodes.Though Figure 93 A and Figure 93 B have shown big continuous, a folding active region (being folded stack 172), are understandable that, can use above-mentioned series connection to realize identical or similar effects with the batteries in parallel connection execution mode.Figure 93 A has shown continuous anode 24 and continuous negative electrode 26, and Figure 93 B has shown a plurality of isolated anodes 24 and negative electrode 26, makes bending area not have electrode material.Identical with Figure 92 B, Figure 93 B is electrically connected isolated electrode and thereby uses insertion conductor 148 series-connected cells 166 that pass electrolyte 28 at bending area.Every kind of execution mode (for example continuous electrode or isolated electrode) may be used to the design that freely suspends.
The advantage of free superposed layer is if having a CTE of composite construction of anode and negative electrode obviously different with the CTE of the remainder (edge, top cover and bottom) of main body, and the zone that then freely suspends allows to disconnect physical connection.Be understandable that, except foldable structure, other fuel cell rod TMInstalling 10 structures also can be formed by this free suspension structure.Figure 94 A has shown the cross section of two parallel connections (opposite with the series connection among Figure 93 A and Figure 93 B) active layers (each layer comprises anode 24, dielectric substrate 28 and negative electrode 26), the sidepiece freedom of this active layer.Figure 94 B has shown along the fuel cell rod of the 94B-94B line intercepting of Figure 94 A TMThe top cross-sectional view of device has shown that active layer is free and be anchored at a side of described device along three sidepieces.This geometry can not increase the complexity of the flow path of gas in the air duct 14 in the superposed layer outside, but can increase the complexity of the flow path in the air duct 20 of gas in superposed layer, this complexity can solve by making gas introduce air duct 20 and change the inner space subsequently over to, pass negative electrode 26 and get back to pottery 29 according to the edge of edge pottery 29 as Figure 94 C and Figure 94 D.
Above-mentioned various execution mode has the advantage of common air or fuel channel, and this has improved density.When gas flow channel is used for the male or female of parallel operation, can edge region or the many places of central region contact these male or females.But in other embodiments, air or fuel channel with the male or female that is used for tandem working may be useful, and in these execution modes, and male or female should electric insulation, to prevent described device short circuit.For this reason, the material on barrier layer 174 can be set in described gas flow channel, with provide between an electrode and another electrode machinery electric insulation shown in the cross section of two negative electrodes 26 among Figure 95.Barrier layer 174 can be continuous or have breach, moves by side to opposite side to allow gas from one.Described barrier layer can exist only in the zone of active anode 24 and negative electrode 26, and perhaps described barrier layer can further be extended along described flow channel in sandwich construction.Barrier layer 174 has prevented the short circuit between the electrode.Barrier layer 174 can be extremely thin, and this can cause some distortion, but as long as it can keep electric insulation.For example, the thickness on barrier layer 174 can be between about 5 μ m to 50 μ m.Can add non-conductive (for example preceding spheres of ceramic of sacrificing in the organic material 72 of zirconia or sintering) to support barrier layer 174, this is with similar with reference to Fig. 7 B, Fig. 7 C and the described mode by cylinder 54 other layers of support of Fig. 7 D.
The execution mode selected of short circuit is at the top of anode 24 or negative electrode 26 insulating barrier 176 to be set, shown in Figure 96 between two anodes 24 that are used to prevent to connect or the negative electrode 26.For example, insulating barrier 176 can be made by for example zirconia or electrolyte.Insulating barrier 176 must be a porous, enters anode 24 or negative electrode 26 to allow gas to pass insulating barrier 176, and must be nonconducting.Below the insulating barrier 176 of this porous, anode 24 or negative electrode 26 still need to have its due performance: pore, conductivity and chemical reaction position.For example, the thickness of insulating barrier 176 can be between about 1 μ m to 25 μ m.
In the high-end applications of multi-layer fuel cell, electrolyte, anode 24 and negative electrode 26 are enough thin, make the distortion behind the sintering become a specific character of material.Deform and insulating barrier 176 plays under the situation of effect in above-mentioned design, then said structure is shown in Figure 97.In this case, because fuel channel 14 or air duct 20 are open along other certain some a little positions of its width, thereby fuel channel 14 or air duct 20 do not have complete pinch confinement.This causes anode 24 or negative electrode 26 contacts, but because at least one insulating barrier 176 is in contact position, so anode 24 or negative electrode 26 can not be short-circuited (promptly electrically contacting).
For fuel cell rod from heat TMDevice 10 transmits electric power, and as surface conductor, its conductivity can be as metal with LSM.For long distance (several inches) transmits electric power, the resistance of LSM helps to reduce power consumption.This power consumption can overcome by forming thicker LSM conductor.For this reason, do not adopt silk screen printing (screen-printing), LSM is cast as LSM is with 178 more usefully, then LSM is with 178 assembling fuel cell rods TMIn device 10 the described structure in top and/or bottom,, respectively shown in the perspective view of the viewgraph of cross-section of Figure 98 A and Figure 98 B.By this method, thickness can (.01 "-.05 ") changes between mil (mil, i.e. mil) is thick to tens at several mil (.001 "-.005 "), and can cover the whole width of described Battery Baton.Make a kind of than thick-layer with other layer during sintering, the CTE of LSM can have problems, and in this case, can sneak into YSZ (with identical in the negative electrode) in LSM, more closely to mate the CTE of entire cell rod.In addition, LSM is non-conductive when low temperature, thereby should be at the fuel cell rod TMThe top of LSM on the zone that is positioned at the stove outside of device 10 is provided with precious metal (for example silver) or other low-temperature conductive material.Though that illustrate is LSM, is understandable that the present invention is not limited only to this.When mentioning LSM, electric conducting material, non-oxidized substance metal or precious metal can use arbitrarily, and therefore, in fact LSM can be made by the material beyond the LSM with 178.
According to another embodiment of the invention, can form the fuel cell rod as conductor with nickel TMThe low resistance of installing 10 ends connects.But as long as there is air, nickel will be in the state of oxidation and nickel oxide is nonconducting.The fuel cell rod TMDevice 10 preferably uses in air because when stove and atmosphere are used, can make whole system simplify more and cost lower.Therefore, use nickel to be to make it to be in reducing condition as the problem of conductor.So, in order to overcome the problem of nickel oxidation, used the inner passage that accommodates nickel conductor 182 180 of the end that extends to described device, and inner passage 180 supplies with and fuel arranged in case oxidation, shown in Figure 99.The conductivity of nickel is lower than platinum, approximately is 6 μ ohm-cm (ohm-cm), so nickel is in the scope of obtainable best conductor (copper, silver).Therefore, in the inner passage 180 that is connected with fuel, occupy certain space, can make nickel be in reducing condition, thereby allow its use by making the nickel conductor.With further reference to Figure 99, at the end of nickel conductor 182 (pipe connect near), nickel conductor 182 can stretch out described device, to be electrically connected with contact mat 44 and connector 134 as shown in prior figures.For example, can use silver to carry out the transition to surrounding air here from reducing atmosphere.Present embodiment is illustrated with reference to the described connector 134 of Figure 67 A to Figure 67 B in conjunction with the front, but is not limited to this.
According to another embodiment of the invention, no matter the multi-layer ceramics fuel cell structure is the fuel cell rod TMDevice 10,100,400,500 is still managed the fuel cell rod TMDevice 200,300, perhaps other multi-layered devices can use the green ceramics fabrication techniques, and permanent subsequently link pipe 184.End pipe 184 can extend to the cold-zone from the hot-zone, can connect the pipe or the air conveying member (for example supply pipe 50) of other form in the cold-zone.Selectively, end pipe 184 can connect fuel and air is supplied with or facility is removed in discharging, and need not to use supply pipe 50.Multi-layered devices (for example installing 10,100,200,300) is positioned at the hot-zone, and 184 permanent connections of end pipe carry out the transition to the cold-zone.Shown in Figure 100 A and Figure 100 B, multilayer (pipe) fuel cell rod TMDevice 10,100,400,500 (200,300) or arbitrarily other fuel cell structure with a plurality of air and fuel channel be provided with special coiling end pipe 186, this coilings end pipe 186 is that end is managed a kind of execution mode of 184.Device 10,100,200,300,400,500 (being anode, negative electrode, electrolyte and fuel channel) form by the whole bag of tricks in this explanation, increase the end pipe 186 of reeling then and connect.Increase the end pipe 186 of reeling by the coiling technology, wherein, described pipe is made by band, will continue then to reel to obtain the end pipe 184 of Len req with reeling enough number of turns so that enough thickness to be provided around the end of described Battery Baton then.In the part that is not supported of end pipe 186 of reeling, need to be provided with mandrel, in this case, can use the interim mandrel that is coated with release agent or wax.Can carry out lamination to the layer of described pipe, to obtain enough intensity and density.Can remove mandrel behind the lamination.The permanent end pipe 184 that connects can provide machinery and electrical connection to active structure.The permanent end pipe that connects 184 is connected with the active structure one basically by sintering together.This provides durability for this designs.Therefore, by the final device of sintering together, the end pipe 184 of connection can sintering on multi-layered devices (for example 10,100,200,300,400,500), thereby integrally formed basically.
End pipe 184 can be made by conductivity ceramics, LSM for example, or make by nickel oxide.On the position that carries out the transition to cold-zone or air, end pipe 184 can be coated with conducting metal or alloy.Can as the band of drawing a picture or reel, apply the cold junction of this metal or alloy and final pipe design.Selectively, the end pipe 186 of replace reeling, end pipe 184 can be by for example rolling or be crushed to.If end pipe 184 is soft, then can connect pottery by lamination under green state.The end pipe 184 of reeling end pipe 186 or increasing also can be the composition of two or more materials.For example, under the situation of using LSM, can in LSM, mix YSZ to help to mate the sintering character of CTE and pure YSZ.
Can form the complicated active structure and the sintering subsequently of multi-layered devices ideally, will hold then and manage 184 and be permanently connected to the end, but there is practical difficulty in this.The shape that makes the end of described device form acceptant pipe connections will be favourable, the device 10 shown in Figure 101 (this device also is illustrated with reference to the cylindrical end that impermanent pipe is connected that is used for of Fig. 3 A and Fig. 3 B).Outboard end that can moulding (for example by machine work) (preferably processing under green state) active device 10 forming the cylindrical end 190 of easy installation ceramic end pipe 184, thereby provides axial connection.For the fuel cell rod that snugly fits in the bigger system TMDevice 10 (or 100,200,300,400,500), the axial connection of end pipe 184 is desirable.
Selectively, fuel cell rod TMThe inboard of end 11a, the 11b of device 10 can be machined as one or more stomidiums 192 that formation can be inserted one or more end pipes 184, shown in Figure 102 A and Figure 102 B.In a lot of designs, it is favourable inserting two or more end pipes 184 side by side.The end pipe 184 of a plurality of insertions can bring convenience for miniaturization (for example being used for hand-held device), or is convenient to the Simplicity in Design in power station.
Can form end during for green compact at two parts (active device 10 and end pipe 184) and manage permanent connection of 184, thereby sintering together, perhaps forever connect behind sintering respectively, perhaps when one sintering and another have been in green compact, forever connect at these two parts.If two parts sintering when connecting then can use glass or glass ceramics (or low frit pottery for example is added with the YSZ of sintering auxiliary ceramic such as alum clay) to form and connect.If two parts link together, then can use laminating method or above-mentioned connection material when green compact.If parts are green compact and another parts sintering, then these methods of attachment can be used.
Be used for the execution mode (being shown in the perspective view of Figure 103 A) that permanent pipe connects according to another kind, can rectangle end 194 be set, and use the rectangular tube 196 of the coupling that is connected in this end, to stretch out described stove at an end of active device.In addition, can make link with the end pipe 184 of matching parts coupling is that rectangle and the other end are for circular.This shape transition end pipe 198 is shown among Figure 103 B, can make by casting or molding.Particularly, this shape transition end pipe 198 can be made the molding ceramic member that meets shape need.Described rectangular end is easy to be laminated on the rectangle end 194, and this ceramic member can be the pipe of circular or other shape with alteration of form then, to carry out the transition to outside the stove.In addition, these pipes and exit passageway can be made by electric conducting material, thereby can realize when realize being electrically connected that gas connects, with the quantity by reducing parts and these parts are played more than a kind of act on the final design of simplifying described system.
In illustrated various execution modes, illustrated and constructed described structure with the green compact band.But, be not to use the green compact band.The another kind of selection is that twine prints all material that uses in the described structure.This need not with use, but obtained looking and arranged closely similar final green compact device.In fact, the very difficult zirconia of distinguishing out the zirconia layer by the setting of twine printing technology and being set to strap.Another modification is to adopt distributor to write described material.In the simplest form, can be pipe, but it will be understood by those skilled in the art that as time passes the continuation development with miniaturization that the exact method of realizing this purpose is maturation more as the pen writing material.Use Writing method can form complicated structure, have less groove and more complicated 3D structure.But in fact, these methods are useful not as the multi-layer ceramics technology.When structure more and more hour, use the pencil of equal number, forming can be elongated than the time of bigger device.Self there is the problem of productivity ratio in this method.It is more practical to use band method or printing process to make described device, and as the current capacitor manufacture method, wherein, a factory produces 1,000,000,000 little chips weekly, and each chip has the layer more than 400.But the present invention has expected this manufacturing fuel cell rod of the present invention TMThe method of device.
In multi-layered devices, also can replace layer with microtubule.In conjunction with the time pipe bigger area can be provided.If multi-layered devices comprises thousands of microtubule, then can be in building process by with these microtubule end-to-end links, connect side by side or form bigger layer group and come in conjunction with these pipes, to obtain voltage.But the complexity of writing becomes the factor that reduces productivity ratio once more.But, in a word, use " design form " according to the present invention to allow this design work.Be somebody's turn to do the device of the present invention that " design form " expression has practical structures, material system wherein can use towards the direction that realizes overall design goal.Because physical structure and material property no-float, described device can allow the violent variations in temperature along the length of described device, allow low temperature and low cost to be connected, simplify the structure and increased durability.
In above-mentioned various execution modes, multilayer anode, negative electrode, electrolyte and gap have been used in " the design form " that be used for SOFC or other fuel-cell device.The ceramic core (nickel oxide, YSZ, LSM or other preferable material) arbitrarily that should " design form " also be used in presintering is gone up the fuel cell rod that makes up TMThe multilayer active structure of device 10,100,200,300, thus for example plate 610, long slab 612, pipe 614 or flat tube 616 structures had, shown in Figure 104.Net shape is similar to previous designs, but manufacture method is from solid material 610,612,614,616, increases the layer (thick film refers to coating cream layer, can be by printing, immerse or write coating) of thick film then on these solid materials.
When using existing flat tube 616 or pipe 614 designs, the middle part of pipe holds a kind of gas, and the outer surface of pipe is exposed to other gas.Multilayer designing requirement gas is changed in 614 designs of flat tube 616 or pipe should be controlled in the pipe.Flat tube is as being used for annotated giving an example.In existing use, can have strutting piece in the flat tube, flow with control air or fuel.Flat tube is a porous, makes it allow gas to be out-diffusion to anode 24, negative electrode 26 and electrolyte 28.A kind of execution mode of strutting piece can be the triangle rib 622 shown in the vertical stratification shown in Figure 105 A (vertical ribs 620) or Figure 105 B for the rib of structural strength is provided.Except having rib, the inside of flat tube 616 only holds a kind of gas in passage 624.As clearly illustrating in the prior art, Figure 106 has shown how to use flat tube that a kind of gas is supplied to an electrode at present.Crooked arrow has shown how gas passes the porous ceramic of described pipe upwards towards first electrode diffusion (if electrode is positioned at the both sides of flat tube, also can spread) down.
According to the present invention, rib 620 is used for passage 624 is divided into two alternate group 624a, 624b, makes some transport fuel (fuel channel 624a) and some transport air (air duct 624b), shown in Figure 107 A to Figure 107 B.In order to reduce cost, these flat tubes can be crushed to, thereby alternate channel 624a, 624b can be in each end 11a, 11b sealings, to allow gas along relative direction alternately mobile (alternating flow).Can seal for example glass or pottery by high-temperature material, if perhaps in the cold-zone of flat tube, can be with for example organic material or silicon sealing of cryogenic material.Selectively, can make described pipe, sealing alternate channel when making by molding.Shown in Figure 108, if desired, can make the first end 11a of each passage 624a, 624b open, thereby air enter and pass adjacent passage 624a, 624b with fuel along identical direction.In this case, described rib need be an atresia, and can not have the defective that allows two kinds of gases to mix.At one end 11a uses connector that correct gas is guided to correct passage 624a or 624b, shown in Figure 108.
In addition, can be coated with application layer 626 (for example glass or ceramic of compact), mobile with the subregion of sealing flat tube thereby control gaseous is passed antipriming pipe, shown in Figure 107 B.Uncoated porous surface then allows suitable gas upwards to be diffused in the suitable passage of multilayer active structure.The surface of sealing porous pipe and permission porous surface are to the suitable suitable gas of zone diffusion, and this dual mode can combination in any.
Selectively, not necessarily must be that the flat tube 616 of porous just can be used for this design, these are different with individual layer flat perforated pipe of the prior art.Alternatively, can form hole (the hereinafter execution mode that illustrates with reference to Figure 109), this hole allows gas to leave passage 624a, 624b and is moved upwards up in the multilayer active structure.Can when being in green state or sintering state, flat tube 616 increase these holes.Flat tube 616 can extend to outside the described stove, make an end 11a folding being used for a kind of gas in the cold-zone easily, and other end 11b is folding to be used for other gas (also at low temperatures), shown in Figure 111 at the other end.Selectively, an end of flat tube (for example Figure 108) can stretch out described stove, and air and fuel can be in cold junction 11a supply to passage 624a, 624b.Can use the complicated connector of the end 11a of coupling pipe 11b, and air and fuel are provided among suitable passage 624a, the 624b.In described stove, the hole in the flat tube 616 can allow gas to be moved upwards up in the multilayer active structure.Gas passage 624b can allow gas flow in the multilayer active structure, and fuel channel 624a can allow fuel to flow in a similar manner.Independent hole can be used for independent layer, and perhaps a hole can be used for a plurality of layers.
In the multilayer active structure, can set up any combination of serial or parallel connection structure, shown in the figure previous drawings.Fuel cell rod of the present invention shown in Figure 109 TMIn the device 600, can make that gas supplied enters via path 628 from flat tube, so that gas rises to suitable layer.Can use various technology and design, for example pillar (column), wall are protruding, offset passageway etc., thereby via path 628 can not extended under flowing gas does not leave the situation of this passage.It should be noted that the heavy line of vertical curve is the display mode that the illustrated content of expression is not positioned at same plane cross section.Figure 110 has shown a kind of selectable method, makes the lateral region distortion of gas passage 14,20 in its extension, thereby makes gas passage converge flat tube 616 downwards.If the surface of thick-film material being added to flat tube 616 then can be simpler to make up the multilayer active structure.
Figure 111 has shown the fuel cell rod of design form TMThe perspective view of device 600, wherein, described stove is stretched out in the end, more specifically, flat tube 616 is arranged in hot-zone 32, and end 11a, the 11b of its opposite end 11a, 11b enter cold-zone 30 (also can select to make an end enter the cold-zone), are built with the multilayer active structure on flat tube 616, and via path 628 is used for making gas upwards to be diffused into the multilayer active structure.Selectively, shown in Figure 112, end 11a, the 11b of flat tube 616 can be positioned at furnace interior and be connected in the high temperature manifold 630 that is used to carry gas.
Variation according to the flat tube 616 of conception form of the present invention is narrow flat tube 632, wherein, passes the zone of furnace wall 96 at flat tube, and the width of this flat tube reduces, shown in Figure 113.Can make the indoor design of narrow flat tube 632 can make narrower end mate the main region of pipe by variety of way.For example, rib is spread out to main region from narrow end, thereby the size of all or some passages 624 increase, and perhaps can make the rib 620,622 of increase be positioned at inside, thereby fluid is diverted in the passage 624 of increase, to supply with more zone.The width of the part of leaving stove by making narrow flat tube 632 is narrower, more difficult cracking.
Here in Shuo Ming the flat tube execution mode,, independent end pipe 184 can be inserted in the stove, to mate flat tube 616 (632) at stomidium 192 places, shown in Figure 114 as the replacement scheme of manifold 630.Pipe 184 is sintering together, can forever connect, and perhaps can connect temporarily and by glass or mechanical pressure.
SOFC goes on well under high temperature (being generally 800 ℃).According to one embodiment of the present invention, can use so-called transparent stove (see-through furnace) to operate fuel cell rod of the present invention easily TMDevice (10,100,200,300,400,500,600).Transparent stove can be the Trans Temp that is made by Thermacraft company TMStove.Pipe furnace is the insulated tube that has heating element in the pipe and have open end.The middle part of pipe furnace can be heated to operating temperature rapidly.In this transparent stove, insulated tube is made by multilayer quartz and/or glass tube, and is normally two-layer but also can be with more multi-layered, and quartz layer can make stove insulate fully and allow the people to see inside.Usually, the inboard of quartz ampoule has small reflection material (for example gold) coating, in unnecessary reflect heat is melted down.Trans Temp TMStove provides electric power by the electricity of the spiral in stove circle.In addition, Trans Temp TMStove can heat by alternate manner, for example gas combustion structure.Use Trans Temp TMStove is as operation fuel cell rod of the present invention TMThe operation format of device makes observes the fuel cell rod of operating easily in pipe furnace TMDevice.
For example, motorcycle can provide electric power by the SOFC technology, and wherein, pipe furnace is positioned at the zone that is generally used for gas cabinet.Also can provide electric power for automobile by this method.To on the engine of new Ferrari Automobile Design, use glass plate so that the people can see that the principle of engine is similar, use the transparent SOFC stove also can be so that people can see the SOFC engine.Perhaps in the house, SOFC can provide electric power and use transparent stove whole house.Before oneth century, fireplace is positioned at the central authorities in house, as the center of heating and culinary art; In modern house, transparent SOFC stove can be positioned at the psychology middle part in house.In Automobile Design, can have more than one transparent stove element.Can be arranged side by side four.Perhaps four elements can form "+" shape.Except aesthetic, the functional factor that is used for the transparent stove design of SOFC is to observe the ability of stove in operate as normal.The fine arts factor of this design can produce positive impact to other design aspect in bigger product or place.
As Trans Temp TMWhen stove was coated with gold, perhaps uncoated when coating is arranged, the color of stove was orange-yellow basically.According to the present invention, can apply the inboard of silicon dioxide (quartz) with different material, perhaps apply silicon dioxide tube, thereby can make color become blueness, green or other color that can imagine arbitrarily.
Therefore, the fuel cell rod of the present invention's design TMIn the device, by having transparent wall 96,96 ' or 96 " furnace structure hot-zone 32 is provided.In addition, can usually apply hot-zone wall 96 or be doped in the hot-zone wall 96 with the unit that hot-zone 32 is sent be not orange-yellow color (for example blue).Can be by combustion fuel or by resistance wire heating furnace (hot-zone) 32.Design is the automobile that electric power is provided by SOFC wholly or in part in addition, wherein, uses transparent stove or a plurality of transparent stove to form the hot-zone 32 of SOFC.In addition the design be to have transparent wall 96,96 ' or 96 ", to the fuel cell rod of small part by this paper TMDevice provides the house heating furnace of electric power.Above-mentioned all about the fuel cell rod TMThe execution mode of device (comprises pipe fuel cell rod TMDevice) can comprise transparent hot-zone 32.
Describe above-mentioned execution mode in detail with reference to SOFC.But these execution modes also can be used for molten carbonate fuel cell (MCFC).The main distinction on the principle is that electrolyte changes fused carbonate (for example lithium carbonate or sodium carbonate) into by zirconia.Carbonate fusion under higher temperature also can be conducted (with CO 3Form) oxonium ion.Fused carbonate remains on porous ceramic (LiAlO for example 2) in capillary in.Anode and negative electrode be all based on the nickel among the MCFC, rather than be generally used for the LSM among the SOFC.Use porous LiAlO 2Replace being used for the structural zirconia of SOFC and making carbonate be positioned at described hole.And in air-flow, add CO 2This design form is promptly according to the fuel cell rod that is used for of the present invention TMThe entire infrastructure of device may be used to MCFC.
The present invention also designs and uses ammonia (NH 3) Battery Baton acts as a fuel TMThe fuel of device.Ammonia can provide H+ ion in anode-side as hydrocarbon or hydrogen.Use the advantage of ammonia to be, with hydrogen type seemingly, can not discharge any CO 2But, use NH 3Shortcoming be poisonous.
The present invention also designs and uses the fuel cell rod TMDevice changes jet engine into electric motor structure, and this can obtain higher fuel efficiency.Use fuel cell rod TMDevice produces engine power can be reduced fuel consumption and be used to fly necessary fuel load.It no longer is called jet engine, and this propelling motor can be called double flow engine (ducted fan), if perhaps do not have the external motor cover then can be called blower fan (fan).According to estimates, if can realize 10MW electric power, then double flow engine can replace the jet engine of Boeing-737.Use the higher 1MW/ft of density value 3The fuel cell rod TMDevice assembly can produce this aircraft power.Can use a plurality of independent unit to produce 10MW, particularly, can use 10 modules, each module produces 1MW.By have the power generation module on wing, these modules can be positioned as close to engine, thereby can reduce the resistance loss in the electric wire.The design selected that makes SOFC be positioned at wing is to make SOFC be positioned at fuselage.The vibration of fuselage is less than the vibration of wing, so fuselage is position more suitably.Can under higher voltage, operate by in transmitting electric power the time to the conduction problem of wing transmitting electric power from fuselage and to be overcome.Perhaps, it is useful using the refractory ceramics superconductor to conduct this segment distance.Therefore,, provide a kind of aircraft that uses electric propulsion system, wherein, produce the electric power that drives this electric propulsion system by a plurality of SOFC modules according to the present invention.Electricity push away a kind of execution mode of system only be blower fan (hood arranged or do not have hood can).In addition, these modules can be positioned in the wing of aircraft.
According to another embodiment of the invention, use the pipe jointing gas passage and the negative electrode of micron-scale or nano-scale, and/or in conjunction with fuel channel and anode.By in conjunction with these features, can make higher power density (KW/L) and firmer fuel cell rod TMDevice.Replace making respectively that being used for the gas passage 14,20 that gas and fuel flows is adjacent to anode 24 and negative electrode 26, can produce flow gap in anode and negative electrode by microtubule or nanotube (the unified micro-/ nano pipe that is called) are set.This can significantly improve the diffusion of gas in anode and negative electrode.At present, anode and negative electrode are porous, and gas passes these hole diffusions.In fact, gas can not spread rapidly, and this may be because of these hole random distribution, thereby air-flow must pass tortuous passage.Be restricted to the passage in anode 24 and the negative electrode 26 or the micro-/ nano pipe in path by setting, it obviously can be than the Kong Gengzhi of the random distribution of anode 24 and negative electrode 26 self and longer, thereby can improve the fuel utilization.
In fact, can in anode and/or cathode material, insert fiber 634.For example, can use carbon fibre material.Fiber can be a pad type cloth 636, thereby the length of fiber is short relatively, distributes also can be pressed into or be pressed in the thin slice at random, shown in the microphoto of Figure 115 A (amplifying 500 times) and Figure 115 B (amplifying 200 times).Ideally, can use the organic cloth or the fabric of any type.Selectively, the long particle that can distribute in electrode cream is to obtain slotted hole behind sintering.The carbon twills are especially useful, because can make most of fiber along preferred flow direction location easily.
In Figure 115 A and Figure 115 B, the diameter of fiber 634 is 5-10 μ m.Can be by making fiber number these diameters littler (being nano-grade size) that make of unit are more.For example, can use the nanotube of diameter as 1-100nm.Selectively, can use the microtubule of diameter as 0.1-100 μ m.Usually, the diameter of pipe can be as small as 1nm or following, and is big to about 100 μ m, for example 50nm to 50 μ m.
Then, can use electrode cream to soak into fiber 634.This electrode cream has been a porous, and comprises that graphite powder is to help to provide the extra hole that is of a size of 0.5-3 μ m.Behind roasting and the sintering, fiber shown in Figure 115 A and Figure 115 B and graphite powder can form the reticulated cell and the micro-/ nano pipe that can increase gap distribution in electrode.For carbon fiber, can in sintering profile process, disappear later at 750 ℃.Figure 116 A to Figure 116 C is the microphoto of the microtubule 638 in the electrode that amplifies after demonstration is formed on sintering, is the carbon fiber of 5-10 μ m by the roasting diameter, forms three different passages in anode 24.
Present embodiment can obtain well distributed fuel and air in anode 24 and negative electrode 26, and allow in anode and cathode zone, to remove fuel channel 14 and air duct 20, because if fuel and air can pass anode and cathode flow then need not to make fuel and air to flow above anode and negative electrode.In addition, if removed the gap of anode and negative electrode top, then anode and negative electrode can touch electrolyte 28 contiguous in the sandwich construction, thereby have significantly improved the intensity of sandwich construction.
It should be understood that and can use micro-/ nano pipe 638 in the multi-layer fuel cell structure arbitrarily, no matter whether this structure has the design form that extends to the cold-zone from the hot-zone.Present embodiment can the side's of being used in plate on, perhaps be used on the tube-surface.Especially it is effective when design has the system of multilayer character or designs the 3D size.
At described multi-layer fuel cell rod TMIn the device, sample can be formed the distance that for example makes between the continuous layer of battery is 0.010 ", promptly distance is 0.010 between electrolyte and the electrolyte ".Be the gap that 10mil comprises 2mil, to be used for fuel or air flows.According to present embodiment,, can make power density (KW/L) significantly increase by 20% by removing the gas flow thickness of this 2mil.But, it should be understood that the micro-/ nano pipe 638 in anode and/or the negative electrode can combine with air/fuel passage (gap), mobile to increase, and can not become the means of removing described gap.
According to the fuel cell rod with hot-zone 32 and at least one cold-zone 30 of the present invention TMThe another kind of execution mode of device, the method that forms fuel channel 14 and air duct 20 make fuel channel 14 and air duct 20 be positioned at passage from the cold-zone to the hot-zone, in the hot-zone, can produce the pore and the micro-/ nano pipe 638 fuel stream that pass in the electrode.The passage of open passage 14,20 (for example 2mil (.002 ")) provide be used to make that gas enters, easily, the passage of low flow resistance.Because the thickness of these passages is identical with the thickness rank of anode 24 and negative electrode 26, thereby open gas flow channel (14,20) can just in time extend to the anode 24 in the hot-zone 32 and the edge of negative electrode 26, shown in Figure 117.If desired, passage 14,20 can be orientated as permission air and fuel and enter anode 24 or negative electrode 26 from sidepiece.Among Figure 117, anode 24 or negative electrode 26 are used to illustrate parallel 28, one electrolyte 28 of two electrolyte and are positioned at anode 24 or negative electrode 26 tops, and another is positioned at the below.In the series design, can between two parts of anode 24 or negative electrode 26, separator 642 be set, shown in Figure 118.Separator 642 can be an insulator, for example zirconia or electrolyte.
In more complicated form, for example to use in the series design of connection electrode 148, this method can be used for once supplying with a plurality of anodes 24 or negative electrode 26.Preferably make single battery short and wide, thereby reduce resistance.Can use micro-/ nano pipe 638 for this reason, because micro-/ nano pipe 638 has higher flow resistance than big gap, thereby this short and wide battery can be worked well, and with the utilization that allows enough gas flow and improve fuel, this is a main target of all fuel cells.Figure 119 has shown a kind of schematic top plan view of series design, illustrates that mainly gas flows into and the outflow battery.In order to be illustrated more clearly in, can use fuel-side to illustrate.Because be vertical view, so the surface of seeing is the surface of anode 24.Electrolyte 28 and anode 26 can't be seen from figure.Arrow represents that fuel flows into anode 24.Fuel enters the sidepiece of anode 24, wherein a part of then fuel-turn electrolyte, and some fuel continue across anode and flow towards fuel outlet 16.In addition, the thickness in the air-flow and the zone of male or female combination is identical and minimize, because fuel channel 14 is provided with anode 24, rather than is positioned at anode 24 tops.
Fuel cell field also needs to be used for the midget plant of low electrical production.For example, army can use the continuous micro power that 20W was provided in 100 hours.For this reason, fuel cell rod TMDevice a kind of design of 700 is to have two bar-shaped inlet 702a, 702b, and this bar-shaped inlet 702a, 702b extend to the big zone 704 of described micro device, but bar-shaped inlet 702a, 702b are from the same side extension, shown in the end view of Figure 120.A bar-shaped inlet 702a is used for air, and another bar-shaped inlet 702b is used for fuel.Big zone 704 is the active regions that are positioned at hot-zone 32.With the fuel cell rod that respectively has an outlet in both sides TMDevice 700 is compared, and all enters from the same side by making gas, can reduce overall volume.In addition, compare with the connected situation that is used for the inlet of air and fuel with having independent long access road, this zone also reduces.The size (area) of the device 700 shown in Figure 120 can be for example 1 square inch, or 3 " * 3 ".
According to another kind of execution mode, the fuel cell rod TMThe big zone 704 of device is divided into a plurality of parts.If fuel cell rod TMDevice is provided with 20 active layers, and then each active layer is filled the big zone shown in Figure 120, and this helps transmitting heat then, to divide this zone.The zone of dividing can be similar to the page or leaf of book.The spine of book (gas supply pipe enters from this) can be an one fully, perhaps separates fully, and perhaps part is separated, respectively shown in the vertical view and perspective view of Figure 121 A and Figure 121 B.
At last, be used to the fuel cell rod that carries TMIn the device 700, on described device, has point of safes 706, shown in Figure 122.Point of safes can be the shape of the ridge 708 that reveals from described device, but only is used to extend in the insulator 98 of micro furnace, and thereby has cushioned vibration and supported fuel cell rod stably TM Device 700.Ridge 708 can form different shape, but ideally, forms little cross section, thereby ridge 708 can not conduct heat go out described device.Ridge 708 can for needle-like improving intensity, and at the fuel cell rod TMHas bigger connector 710 on the main body of device 700.In addition, stability ridge 708 can be used for any one execution mode of this paper explanation, and no matter whether described device is portable unit.
Though by illustrating that one or more execution modes have illustrated the present invention, and these execution modes have been carried out quite detailed explanation, but these explanations are not limited to or by any way the scope of subsidiary claim is defined as the details of above-mentioned execution mode.To those skilled in the art, extra advantage and modification are conspicuous.Therefore, the wide in range aspect of the present invention is to be not limited to illustrate the embodiment with illustrated detail, exemplary apparatus and method and elaboration.Therefore, under the situation of the scope that does not break away from basic principle of the present invention, can break away from these details.

Claims (59)

1. fuel-cell device, this fuel-cell device comprises:
Ceramic support structure, this ceramic support structure has reaction zone, and this reaction zone is configured to be heated to the working reaction temperature, and has first active layer and second active layer in this reaction zone;
First active cell in described first active layer, this first active cell comprise the first anode, first negative electrode and first electrolyte between this first anode and first negative electrode;
Second active cell in described second active layer, this second active cell comprise second plate, second negative electrode and second electrolyte between this second plate and second negative electrode; And
Electrical connector between a pair of identical electrode, wherein, this is the described first anode and second plate to identical electrodes or is described first negative electrode and second negative electrode, and wherein, this comprises parallel portion and bend to identical electrodes, and this parallel portion to identical electrodes is physically spaced apart, and this bend to identical electrodes physically electrically contacts, described bend forms described electrical connector, thereby with described first active cell and the second active cell parallel connection.
2. fuel-cell device according to claim 1, wherein, described ceramic support structure is a slender substrate, the length of this slender substrate is full-size, so that the thermal coefficient of expansion of this slender substrate only has and the common main shaft that extends of described length.
3. fuel-cell device according to claim 2, wherein, described reaction zone is provided with along the first of described length, and wherein, described ceramic support structure also comprises at least one cold-zone, this at least one cold-zone is along the second portion setting of described length, and the temperature of the working reaction temperature of this at least one cold-zone when being configured to remain below described reaction zone and being heated.
4. fuel-cell device according to claim 3, wherein, the described first anode, second plate and first negative electrode, second negative electrode have the electric pathway that extends to described at least one cold-zone separately, to be electrically connected under the low temperature that is lower than described working reaction temperature.
5. fuel-cell device according to claim 1, this fuel-cell device also comprises:
The 3rd active cell in described second active layer, the 3rd active cell comprise third anode, the 3rd negative electrode and the 3rd electrolyte between this third anode and the 3rd negative electrode; And
Part is connected in series, this part that is connected in series comprises the electric conducting material between a pair of phase different electrode, wherein this is described second plate and the 3rd negative electrode to the phase different electrode or is described second negative electrode and third anode, thereby described second active cell and the 3rd active cell are connected in described second active layer.
6. fuel-cell device according to claim 1, this fuel-cell device also comprises gas passage, this gas passage is opened described a pair of identical electrode separation at described parallel portion place.
7. fuel cell system, this fuel cell system comprises:
The chamber, hot-zone;
A plurality of fuel-cell devices according to claim 4, each described fuel-cell device are orientated as and are made described first be arranged in chamber, described hot-zone, and described at least one cold-zone extends to described hot-zone outdoor;
Thermal source, this thermal source are connected to chamber, described hot-zone, and are suitable for indoor in described hot-zone described reaction zone being heated to described working reaction temperature;
The negative voltage connector, this negative voltage connector is arranged in described at least one cold-zone, and electrically contacts with the electric pathway of the described first anode and second plate; And
The positive voltage connector, this positive voltage connector is arranged in described at least one cold-zone, and electrically contacts with the electric pathway of described first negative electrode and second negative electrode.
8. fuel cell system according to claim 7, this fuel cell system also comprises:
The first anode of each fuel-cell device in the fuel channel, this fuel channel and described a plurality of fuel-cell devices is connected with second plate, and described fuel channel extends through described reaction zone from described at least one cold-zone;
First negative electrode of each fuel-cell device in the oxidant channel, this oxidant channel and described a plurality of fuel-cell devices is connected with second negative electrode, and described oxidant channel extends through described reaction zone from described at least one cold-zone;
The supply of fuel part, this supply of fuel part is connected to each cold-zone in described at least one cold-zone in described hot-zone outdoor, and is communicated with described fuel channel fluid, so that fuel stream is supplied in the described fuel channel;
Air supply spare, this air supply spare is connected to each cold-zone in described at least one cold-zone in described hot-zone outdoor, and is communicated with described oxidant channel fluid, so that air stream is supplied in the described oxidant channel.
9. fuel-cell device, this fuel-cell device comprises:
Ceramic support structure, this ceramic support structure has reaction zone, and this reaction zone is configured to be heated to the working reaction temperature, and has first active layer at least in this reaction zone;
First active cell in described first active layer, this first active cell comprises first negative electrode and the first anode, this first anode comprises the first atresia anode part and the first porous anode part relative with described first negative electrode;
Second active cell in described first active layer, this second active cell is adjacent to described first active cell, and comprise that the second plate and second negative electrode, described second negative electrode comprise the second atresia cathode portion and the second porous cathode part relative with described second plate;
Ceramic electrolyte in described first active layer, this ceramic electrolyte is between the described first anode and described first negative electrode and between described second plate and described second negative electrode;
Wherein, the described first atresia anode part is electrically connected in described ceramic support structure with the described second atresia cathode portion, thereby described first active cell and described second active cell in described first active layer are connected.
10. fuel-cell device according to claim 9, wherein, described ceramic support structure is a slender substrate, and the length of this slender substrate is full-size, so that the thermal coefficient of expansion of this slender substrate only has and the common main shaft that extends of described length.
11. fuel-cell device according to claim 10, wherein, described reaction zone is provided with along the first of described length, and wherein, described ceramic support structure also comprises at least one cold-zone, this at least one cold-zone is along the second portion setting of described length, and the temperature of the working reaction temperature of this at least one cold-zone when being configured to remain below described reaction zone and being heated.
12. fuel-cell device according to claim 11, wherein, the described first anode, second plate and first negative electrode, second negative electrode have the electric pathway that extends to described at least one cold-zone separately, to be electrically connected under the low temperature that is lower than described working reaction temperature.
13. fuel-cell device according to claim 9, wherein, the described first atresia anode part also contacts with the described second atresia cathode portion direct physical.
14. fuel-cell device according to claim 9, wherein, described first active cell and described second active cell separate in described first active layer, and described ceramic electrolyte extends between described first active cell and described second active cell with as medial support structures, and wherein, described electrical connection is formed by conductive path, and this conductive path extends through the described medial support structures between described first atresia anode part and the described second atresia cathode portion.
15. fuel-cell device according to claim 9, wherein, described first active cell and described second active cell separate in described first active layer, and described ceramic electrolyte extends between described first active cell and described second active cell with as medial support structures, and wherein, described electrical connection is formed by electric-conductor, and this electric-conductor extends through the slit in the described medial support structures between described first atresia anode part and the described second atresia cathode portion.
16. a fuel cell system, this fuel cell system comprises:
The chamber, hot-zone;
A plurality of fuel-cell devices according to claim 12, each this fuel-cell device are orientated as and are made described first be arranged in chamber, described hot-zone, and described at least one cold-zone extends to described hot-zone outdoor;
Thermal source, this thermal source are connected to chamber, described hot-zone, and are suitable for indoor in described hot-zone described reaction zone being heated to described working reaction temperature;
The negative voltage connector, this negative voltage connector is arranged in described at least one cold-zone, and electrically contacts with the electric pathway of the described first anode and second plate; And
The positive voltage connector, this positive voltage connector is arranged in described at least one cold-zone, and electrically contacts with the electric pathway of described first negative electrode and second negative electrode.
17. fuel cell system according to claim 16, this fuel cell system also comprises:
The first anode of each fuel-cell device in the fuel channel, this fuel channel and described a plurality of fuel-cell devices is connected with second plate, and described fuel channel extends through described reaction zone from described at least one cold-zone;
First negative electrode of each fuel-cell device in the oxidant channel, this oxidant channel and described a plurality of fuel-cell devices is connected with second negative electrode, and described oxidant channel extends through described reaction zone from described at least one cold-zone;
The supply of fuel part, this supply of fuel part is connected to each cold-zone in described at least one cold-zone in described hot-zone outdoor, and is communicated with described fuel channel fluid, so that fuel stream is supplied in the described fuel channel; And
Air supply spare, this air supply spare is connected to each cold-zone in described at least one cold-zone in described hot-zone outdoor, and is communicated with described oxidant channel fluid, so that air stream is supplied in the described oxidant channel.
18. a fuel-cell device, this fuel-cell device comprises:
Ceramic support structure, this ceramic support structure has reaction zone, and this reaction zone is configured to be heated to the working reaction temperature, and has first active layer at least in this reaction zone;
Ceramic electrolyte layer in described first active layer;
Isolated a plurality of first electrodes in described first active layer, these a plurality of first electrodes are positioned at first side of described ceramic electrolyte layer;
Isolated a plurality of second electrodes in described first active layer, these a plurality of second electrodes are positioned at second side of described ceramic electrolyte layer, wherein, the polarity of described first electrode is opposite with the polarity of described second electrode, be respectively male or female, and wherein, in in described isolated a plurality of first electrodes each and described isolated a plurality of second electrodes corresponding one relative, and described ceramic electrolyte layer is between this relative first electrode and second electrode, the every pair of first relative electrode and second electrode form active cell, thereby are distributed with a plurality of isolated active cells on described first active layer;
A plurality of electric-conductors, these a plurality of electric-conductors extend between described a plurality of isolated active cells, wherein, in described a plurality of electric-conductor each contacts with the first electrode physics of an active cell, and extend through described ceramic electrolyte layer in the space that is adjacent to this active cell, and contact, thereby with the described a plurality of active cells series connection in described first active layer with the second electrode physics of the active cell of adjacent spaces.
19. fuel-cell device according to claim 18, this fuel-cell device also comprises one or more extra active layers, this extra active layer is identical with described first active layer, and with the spaced relationship alternating polarity be layered on this first active layer, wherein, in first gas passage and described a plurality of isolated first electrode each is adjacent, in second gas passage and described a plurality of isolated second electrode each is adjacent, thereby formation spaced relationship, wherein, a plurality of isolated first electrode of adjacent active layer is relative with first gas passage of sharing therebetween, and a plurality of isolated second electrode of adjacent active layer is relative with second gas passage of sharing therebetween.
20. fuel-cell device according to claim 19, this fuel-cell device also comprises first electrical connector and second electrical connector, between described first electrical connector every pair in relative a plurality of isolated first electrode of adjacent active layer, between described second electrical connector every pair in relative a plurality of isolated second electrode of adjacent active layer, thereby with described first active layer and described extra active layer parallel connection.
21. fuel-cell device according to claim 20, wherein, described first electrode and second electrode and described first electrical connector and second electrical connector are porous, and described first electric-conductor and second electric-conductor are atresias.
22. fuel-cell device according to claim 21, wherein, each described first electrical connector comprises each the part in relative a plurality of isolated first electrode of adjacent active layer, the part of this first electrode extends to carries out the physics contact in the described first shared gas passage and in this first gas passage, and wherein, each described second electrical connector comprises each the part in relative a plurality of isolated second electrode of adjacent active layer, and the part of this second electrode extends to carries out the physics contact in the described second shared gas passage and in this second gas passage.
23. fuel-cell device according to claim 18, wherein, described ceramic support structure is a slender substrate, and the length of this slender substrate is full-size, so that the thermal coefficient of expansion of this slender substrate only has and the common main shaft that extends of described length.
24. fuel-cell device according to claim 23, wherein, described reaction zone is provided with along the first of described length, and wherein, described ceramic support structure also comprises at least one cold-zone, this at least one cold-zone is along the second portion setting of described length, and the temperature of the working reaction temperature of this at least one cold-zone when being configured to remain below described reaction zone and being heated.
25. fuel-cell device according to claim 24, wherein, described first electrode and second electrode have the electric pathway that extends to described at least one cold-zone separately, to be electrically connected under the low temperature that is lower than described working reaction temperature.
26. fuel-cell device according to claim 18, wherein, described ceramic support structure is elongated screw winding tubular structure, this screw winding tubular structure has the length of extending between first end and second end, and have outer coiling edge and interior coiling edge, wherein, the described active cell of connecting in described first active layer is arranged in described first and the second portion, described first and described first end are contiguous, described second portion and described second end are contiguous, in described first and the second portion each is included in isolated active cell between described outer coiling edge and the described interior coiling edge, and wherein, the electric pathway that is used for described active cell outside described the coiling edge along the first of active cell extend inward in a spiral manner described in the coiling edge, then along the second portion of described active cell extend outwardly in a spiral manner described outside the coiling edge.
27. fuel-cell device according to claim 26, this fuel-cell device also comprises:
A plurality of first gas passages, these a plurality of first gas passages extend to first discharge-channel adjacent with described second end along described length from described first end, each described first gas passage is delivered to first gas described first electrode of the active cell in each first and the second portion by described first end, described first discharge-channel from described in adjacent described first gas passage in coiling edge extend to described outside the coiling edge, to discharge described first gas; And
A plurality of second gas passages, these a plurality of second gas passages extend to second discharge-channel adjacent with described first end along described length from described second end, each described second gas passage is delivered to second gas described second electrode of the active cell in each first and the second portion by described second end, described second discharge-channel from described in adjacent described second gas passage in coiling edge extend to described outside the coiling edge, to discharge described second gas.
28. fuel-cell device according to claim 18, wherein, described ceramic support structure is elongated screw winding tubular structure, this screw winding tubular structure has the length of extending between first end and second end, and have outer coiling edge and interior coiling edge, wherein, the described active cell of in described first active layer, connecting outside described the coiling edge and described in extend between the coiling edge, and it is spaced apart between described first end and second end, and wherein, the electric pathway of described active cell extends to described second end from described first end.
29. fuel-cell device according to claim 28, this fuel-cell device also comprise with the first conduction end of the first end one of described ceramic support structure and with the second conduction end of the second end one of described ceramic support structure, wherein, described electric pathway also extends to the described first conduction end and the second conduction end.
30. fuel-cell device according to claim 28, this fuel-cell device also comprises:
First access road, this first access road extends to adjacent with described second end from described first end adjacent with described interior coiling edge along described length, a plurality of first gas passages from described first access road extend to described outside the coiling edge, described first access road is supplied to described first gas passage with first gas, each described first gas passage is supplied to first electrode of each active cell with described first gas, and coiling edge discharges outside described; And
Second access road, this second access road extends to adjacent with described first end from described second end adjacent with described interior coiling edge along described length, a plurality of second gas passages from described second access road extend to described outside the coiling edge, described second access road is supplied to described second gas passage with second gas, each described second gas passage is supplied to second electrode of each active cell with described second gas, and coiling edge discharges outside described.
31. a fuel cell system, this fuel cell system comprises:
The chamber, hot-zone;
A plurality of fuel-cell devices according to claim 25, each this fuel-cell device are orientated as and are made described first be arranged in chamber, described hot-zone, and described at least one cold-zone extends to described hot-zone outdoor;
Thermal source, this thermal source are connected to chamber, described hot-zone, and are suitable for being heated to described working reaction temperature with being positioned at the indoor described reaction zone in described hot-zone;
The negative voltage connector, this negative voltage connector is arranged in described at least one cold-zone, and with electrically contact as described first electrode of anode or the electric pathway of second electrode; And
The positive voltage connector, this positive voltage connector is arranged in described at least one cold-zone, and with electrically contact as described first electrode of negative electrode or the electric pathway of second electrode.
32. fuel cell system according to claim 24, this fuel cell system also comprises:
First electrode or second electrode as anode of each fuel-cell device in the fuel channel, this fuel channel and described a plurality of fuel-cell devices are connected, and described fuel channel extends through described reaction zone from described at least one cold-zone;
First electrode or second electrode as negative electrode of each fuel-cell device in the oxidant channel, this oxidant channel and described a plurality of fuel-cell devices are connected, and described oxidant channel extends through described reaction zone from described at least one cold-zone;
The supply of fuel part, this supply of fuel part is connected to each cold-zone in described at least one cold-zone in described hot-zone outdoor, and is communicated with described fuel channel fluid, so that fuel stream is supplied to described fuel channel; And
Air supply spare, this air supply spare is connected to each cold-zone in described at least one cold-zone in described hot-zone outdoor, and is communicated with described oxidant channel fluid, so that air stream is supplied to described oxidant channel.
33. a fuel-cell device, this fuel-cell device comprises:
Ceramic support structure, this ceramic support structure have header field and bottom part, and have reaction zone, and this reaction zone is configured to be heated to the working reaction temperature;
Continuous active layer, this continuous active layer comprises first electrode layer, this first electrode layer is separated with opposite polarity the second electrode lay mutually by ceramic electrolyte layer, and extend to second end from first end in the zigzag mode, described first end is connected on the described header field or is positioned near the described header field, described second end is connected described bottom and partly goes up or be positioned near the described bottom part, and the mid portion between described first end and second end comprises the active cell part between first bend and second bend;
First gas passage and second gas passage, this first gas passage are between active cell part and adjacent with described first electrode layer, and described second gas passage is between the active cell part and adjacent with described the second electrode lay;
Wherein, at least one in described first bend or described second bend not with described header field and described bottom part between ceramic support structure be connected.
34. fuel-cell device according to claim 33, wherein, each described first bend all is not connected with described ceramic support structure with second bend.
35. fuel-cell device according to claim 33, wherein, described first bend is not connected with described ceramic support structure, and the ceramic support structure between described second bend and described header field and the bottom part is connected.
36. fuel-cell device according to claim 33, wherein, described first electrode layer and the second electrode lay comprise a plurality of isolated electrodes separately, these a plurality of isolated electrodes with relativeness along the ceramic electrolyte layer setting in the described active cell part, and described first bend and second bend are arranged in the space between the described isolated electrode, wherein, also comprise a plurality of electric-conductors, wherein, each electric-conductor contacts with the first electrode physics of an active cell part, and extend through in first adjacent bend or the ceramic electrolyte layer in second bend, and contact with the adjacent active cell second electrode physics partly, thereby described a plurality of active cells are partly connected.
37. a fuel-cell device, this fuel-cell device comprises:
Ceramic support structure, has at least one active layer in this ceramic support structure, and be configured in being in the chamber of reaction temperature, work, wherein, described at least one active layer comprises electrolyte between anode, negative electrode, described anode and the negative electrode, the fuel channel adjacent with described anode and the oxidant channel adjacent with described negative electrode; And
At least one elongated ceramic end pipe; This at least one elongated ceramic end pipe has cold junction and hot junction; It is outer to be lower than the temperature work of described reaction temperature that described cold junction is configured to be positioned at chamber; Described hot junction for good and all is connected in the end of described ceramic support structure; Described at least one elongated ceramic end pipe is configured to supply a gas to the one or both in described fuel channel and the oxidant channel; And the length of described at least one elongated ceramic end pipe is full-size; So that thermal coefficient of expansion only has and the common main shaft that extends of described length
Wherein, described at least one elongated ceramic end pipe by following a kind of method or its in conjunction with and for good and all be connected in described ceramic support structure:
The co-sintered under green state with described at least one elongated ceramic end pipe and described ceramic support structure,
Described at least one elongated ceramic end pipe is sintered to the described ceramic support structure of sintering state from green state,
Described ceramic support structure is sintered to described at least one elongated ceramic end pipe of sintering state from green state, perhaps
Between the described ceramic support structure of described at least one elongated ceramic end Guan Yuyi sintering state of sintering state, apply glass bond or glass ceramics bonding agent, and this described bonding agent between the two of sintering.
38. according to the described fuel cell of claim 37, wherein, on end by the pottery band being wound into described ceramic support structure and the elongated interim axle, and should be laminated on this end and the interim axle and sintering by pottery band twister, thereby form described at least one elongated ceramic end pipe from green state.
39. according to the described fuel cell of claim 38, wherein, described end is in green state in described winding process, thereby described pottery band twister and described end are co-sintered, form whole permanent connection with between.
40. according to the described fuel cell of claim 37, wherein, by with the ceramic material molding of green state or be cast as required form and form described at least one elongated ceramic end pipe, and the hot junction of described at least one elongated ceramic end pipe has fit shapes, the corresponding fit shapes of the end of this fit shapes and described ceramic support structure is complementary, and wherein said permanent connection comprises the described fit shapes of connection.
41. according to the described fuel cell of claim 37, wherein, described at least one elongated ceramic end pipe comprises electric-conductor, this electric-conductor is enough to provide and being electrically connected of described anode and/or negative electrode.
42. according to the described fuel cell of claim 37, wherein, described at least one elongated ceramic end pipe comprises the supply of fuel end pipe and the oxidant feed end pipe that is configured to provide to described oxidant channel oxygen-containing gas that is configured to provide to described fuel channel fuel.
43. according to the described fuel cell of claim 42, wherein, described supply of fuel end pipe comprises anode conducting spare, this anode conducting spare extends to described cold junction from described hot junction, and be enough to provide and being electrically connected of described anode, described oxidant feed end pipe comprises the negative electrode electric-conductor, and this negative electrode electric-conductor extends to described cold junction from described hot junction, and is enough to provide and being electrically connected of described negative electrode.
44. a fuel cell system, this fuel cell system comprises:
The chamber, hot-zone;
A plurality of fuel-cell devices according to claim 33, each described fuel-cell device orientates that to make that the first that comprises described hot junction of described at least one elongated ceramic end pipe and described ceramic support structure are positioned at described hot-zone indoor as, and the second portion that comprises described cold junction of described at least one elongated ceramic end pipe extends to described hot-zone outdoor;
Thermal source, this thermal source are connected to chamber, described hot-zone, and are suitable for being heated to described working reaction temperature with being positioned at indoor described at least one active layer in described hot-zone;
Supply of fuel part and oxidant delivery member, this supply of fuel part and oxidant delivery member are connected to the described cold junction of described at least one elongated ceramic end pipe in described hot-zone outdoor, and described supply of fuel part is communicated with so that fuel stream is supplied to described fuel channel with described fuel channel fluid, and described oxidant delivery member is communicated with so that air stream is supplied to described oxidant channel with described oxidant channel fluid.
45. a fuel cell system, this fuel cell system comprises:
The chamber, hot-zone;
A plurality of according to the described fuel-cell device of claim 43, each described fuel-cell device orientates that to make that the first that comprises described hot junction of the first that comprises described hot junction of described supply of fuel end pipe, described oxidant feed end pipe and described ceramic support structure are positioned at described hot-zone indoor as, and the second portion that comprises described cold junction of the second portion that comprises described cold junction of described supply of fuel end pipe and described oxidant feed end pipe extends to described hot-zone outdoor;
Thermal source, this thermal source are connected to chamber, described hot-zone, and are suitable for indoor in described hot-zone described at least one active layer being heated to described working reaction temperature;
The supply of fuel part, this supply of fuel part is connected in the described cold junction of described supply of fuel end pipe in described hot-zone outdoor, and is communicated with so that fuel stream is supplied to described fuel channel with described fuel channel fluid;
The oxidant delivery member, this oxidant delivery member is connected in the described cold junction of described oxidant feed end pipe in described hot-zone outdoor, and is communicated with so that oxidant stream is supplied to described oxidant channel with described oxidant channel fluid;
The negative voltage connector, this negative voltage connector is connected in described anode conducting spare at the cold junction of described supply of fuel end pipe; And
The positive voltage connector, this positive voltage connector is connected in described negative electrode electric-conductor at the cold junction of described oxidant feed end pipe.
46. a fuel-cell device, this fuel-cell device comprises:
Elongated ceramic flat tube, the width of this elongated ceramic flat tube is greater than height, and have a plurality of fuel passage and an a plurality of oxidant path that between first end and second end, extends along direction of elongate, this path is separated by internal rib, and this internal rib is configured to prevent that fuel and oxidant from mixing between described path;
The multilayer active structure, this multilayer active structure is connected on the plane of described elongated ceramic flat tube, this multilayer active structure comprises at least two active layers, each active layer comprises at least one active cell, this active cell has electrolyte between anode, negative electrode, described anode and the negative electrode, the fuel channel adjacent with described anode and the oxidant channel adjacent with described negative electrode
Wherein, the described fuel channel fluid of each active cell is communicated in a plurality of fuel passage of described elongated ceramic flat tube, and wherein, the described oxidant channel fluid of each active cell is communicated in a plurality of oxidant paths of described elongated ceramic flat tube, thereby fuel gas and oxidant gas are configured to be provided to respectively described fuel passage and oxidant path, enter described fuel channel and oxidant channel then respectively.
47. according to the described fuel-cell device of claim 46, wherein, described fuel passage and oxidant path respectively with described fuel channel and oxidant channel between described fluid be communicated with the porous ceramic film material that comprises on the plane that is positioned at described elongated ceramic flat tube, this porous ceramic film material allows fuel gas and oxidant gas to diffuse to fuel channel and oxidant channel respectively from each fuel passage and oxidant path.
48. according to the described fuel-cell device of claim 46, wherein, described fuel passage and oxidant path respectively with described fuel channel and oxidant channel between described fluid be communicated with the circulation path that comprises by the plane of described elongated ceramic flat tube.
49. according to the described fuel-cell device of claim 46, wherein, described elongated ceramic flat tube comprises the mid portion between described first end and described second end, described multilayer active structure is connected on the described mid portion, and described mid portion is configured to be heated to reaction temperature in chamber, and wherein, in described first end and described second end at least one is configured to extend to the outside of described chamber, to be connected to fuel gas delivery member and oxidant gas delivery member under the temperature of described reaction temperature being lower than.
50. according to the described fuel-cell device of claim 49, wherein, in described first end and described second end each is configured to extend to the outside of described chamber, described first end being connected to the supply of fuel part being lower than under the temperature of described reaction temperature, and described second end is connected to the oxidant delivery member being lower than under the temperature of described reaction temperature.
51. according to the described fuel-cell device of claim 50, wherein, the width dimensions of each in described first end and described second end narrows down in the zone that this first end and second end are configured to reach described chamber outside.
52. according to the described fuel-cell device of claim 46, this fuel-cell device also comprises a plurality of independently elongated tubulars, each pipe is configured to an end and is connected in described a plurality of fuel passage and the oxidant path one, and the other end is connected to corresponding supply of fuel part or oxidant delivery member, described independently pipe is configured to pass the chamber wall of chamber, and described chamber is suitable for described multilayer active structure is heated to reaction temperature.
53. according to the described fuel-cell device of claim 52, wherein, described independently pipe is for forever being connected to the earthenware of each fuel passage and oxidant path, and described permanent connection is by realizing described earthenware and described elongated ceramic flat tube co-sintered to form whole tubular construction.
54. fuel-cell device, this fuel-cell device comprises multilayer active cell structure, this multilayer active cell structure has: a plurality of anode layers that alternately pile up with a plurality of cathode layers, comprise a plurality of first microtubules and/or nanotube channel in each described anode layer, each described cathode layer comprises a plurality of second microtubules and/or nanotube channel; And the dielectric substrate that each anode layer and cathode layer that each replaces are separated, thereby described anode layer in the inside of described multilayer active cell structure and cathode layer are used for two adjacent dielectric substrates separately.
55. according to the described fuel-cell device of claim 54, this fuel-cell device also comprises: ceramic support structure, this ceramic support structure comprise described multilayer active cell structure; Fuel channel, this fuel channel extend through described ceramic support structure and extend to described multilayer active cell structure, and are connected in described anode layer, to supply fuel to described a plurality of first microtubule and/or nanotube channel; And oxidant channel, this oxidant channel extends through described ceramic support structure and extends to described multilayer active cell structure, and is connected in described cathode layer, oxidant gas is supplied to described a plurality of second microtubule and/or nanotube channel.
56. according to the described fuel-cell device of claim 55, wherein, described ceramic support structure is a slim-lined construction, this slim-lined construction has at least one cold junction part and is provided with the hot-zone part of described multilayer active cell structure, wherein, described fuel channel and oxidant channel partly extend to described hot-zone part from described at least one cold junction.
57. according to the described fuel-cell device of claim 54, wherein, described a plurality of first microtubule and/or nanotube channel and described a plurality of second microtubule and/or nanotube channel form by the following method, promptly in the fibre plate of expendable material, inject each porous anode material or cathode material, bake this fibre plate to burn described expendable material, carry out sintering then.
58. fuel-cell device, this fuel-cell device comprises ceramic support structure, this ceramic support structure comprises multilayer active cell structure, this multilayer active cell structure has a plurality of anode layers, a plurality of cathode layers, the dielectric substrate that each anode layer and each cathode layer are separated, active fuel passage that forms as one with each anode layer and the active oxidizer passage that forms as one with each cathode layer, described ceramic support structure also has outward extending first elongate articles in an edge and second elongate articles from described multilayer active cell structure, described first elongate articles has the fuel feed passage that is connected in described active fuel passage, and described second elongate articles has the oxidant service duct that is connected in described active oxidizer passage.
59. a fuel cell system, this fuel cell system comprises:
The chamber, hot-zone, this chamber, hot-zone has chamber wall;
According to the described fuel-cell device of claim 58, this fuel-cell device orientates that to make that described multilayer active cell structure is positioned at described hot-zone indoor as, and described first elongate articles and described second elongate articles extend through described chamber wall and extend to described hot-zone outdoor;
A plurality of stabilizing members, these a plurality of stabilizing members extend in the described chamber wall from the described ceramic support structure around described multilayer active cell structure;
Thermal source, this thermal source are connected to chamber, described hot-zone, and are suitable for being heated to the working reaction temperature with being positioned at the indoor described multilayer active cell structure in described hot-zone.
CN200880115271A 2007-11-08 2008-11-08 Multilayered sofc device on ceramic support structure Pending CN101855759A (en)

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